Organic compositions

ABSTRACT

The present invention provides a composition comprising: (a) dielectric material; and (b) porogen comprising at least two fused aromatic rings wherein each of the fused aromatic rings has at least one alkyl substituent thereon and a bond exists between at least two of the alkyl substituents on adjacent aromatic rings. Preferably, the dielectric material is a composition comprising (a) thermosetting component comprising (1) optionally monomer of Formula I as set forth below and (2) at least one oligomer or polymer of Formula II as set forth below where Q, G, h, I, I, and w are as set forth below and (b) porogen. Preferably, the porogen is selected from the group consisting of unfunctionalized polyacenaphthylene homopolymer, functionalized polyacenaphthylene homopolymer, polyacenaphthylene copolymer, polynorbornene, polycaprolactone, poly(2-vinylnaphthalene), vinyl anthracene, polystyrene, polystyrene derivatives, polysiloxane, polyester, polyether, polyacrylate, aliphatic polycarbonate, polysulfone, polylactide, and blends thereof. The present compositions are particularly useful as dielectric substrate material in microchips, multichip modules, laminated circuit boards, and printed wiring boards.

BENEFIT OF PENDING APPLICATION

This application claims the benefit of pending commonly assigned provisional patent applications 60/294,864 filed May 30, 2001; 60/350,187 filed Jan. 15, 2002; 60/350,557 filed Jan. 22, 2002; 60/353,011 filed Jan. 30, 2002; 60/376,219 filed Apr. 29, 2002; and 60/378,424 filed May 7, 2002, incorporated herein in their entirety.

FIELD OF THE INVENTION

The present invention relates to semiconductor devices, and in particular, to semiconductor devices having an organic low dielectric constant material and processes for the manufacture thereof.

BACKGROUND OF THE INVENTION

In an effort to increase the performance and speed of semiconductor devices, semiconductor device manufacturers have sought to reduce the linewidth and spacing of interconnects while minimizing the transmission losses and reducing the capacitative coupling of the interconnects. One way to diminish power consumption and reduce capacitance is by decreasing the dielectric constant (also referred to as “k”) of the insulating material, or dielectric, that separates the interconnects. Insulator materials having low dielectric constants are especially desirable, because they typically allow faster signal propagation, reduce capacitance and cross talk between conductor lines, and lower voltages required to drive integrated circuits.

Since air has a dielectric constant of 1.0, a major goal is to reduce the dielectric constant of insulator materials down to a theoretical limit of 1.0, and several methods are known in the art for reducing the dielectric constant of insulating materials. These techniques include adding elements such as fluorine to the composition to reduce the dielectric constant of the bulk material. Other methods to reduce k include use of alternative dielectric material matrices. Another approach is to introduce pores into the matrix.

Therefore, as interconnect linewidths decrease, concomitant decreases in the dielectric constant of the insulating material are required to achieve the improved performance and speed desired of future semiconductor devices. For example, devices having interconnect linewidths of 0.13 or 0.10 micron and below seek an insulating material having a dielectric constant (k)<3.

Currently silicon dioxide (SiO₂) and modified versions of SiO₂, such as fluorinated silicon dioxide or fluorinated silicon glass (hereinafter FSG) are used. These oxides, which have a dielectric constant ranging from about 3.5–4.0, are commonly used as the dielectric in semiconductor devices. While SiO₂ and FSG have the mechanical and thermal stability needed to withstand the thermal cycling and processing steps of semiconductor device manufacturing, materials having a lower dielectric constant are desired in the industry.

Methods used to deposit dielectric materials may be divided into two categories: spin-on deposition (hereinafter SOD) and chemical vapor deposition (hereinafter CVD). Several efforts to develop lower dielectric constant materials include altering the chemical composition (organic, inorganic, blend of organic/inorganic) or changing the dielectric matrix (porous, non-porous). Table I summarizes the development of several materials having dielectric constants ranging from 2.0 to 3.5. (PE=plasma enhanced; HDP=high-density plasma) However, the dielectric materials and matrices disclosed in the publications shown in Table 1 fail to exhibit many of the combined physical and chemical properties desirable and even necessary for effective dielectric materials, such as higher mechanical stability, high thermal stability, high glass transition temperature, high modulus or hardness, while at the same time still being able to be solvated, spun, or deposited on to a substrate, wafer, or other surface. Therefore, it may be useful to investigate other compounds and materials that may be used as dielectric materials and layers, even though these compounds or materials may not be currently contemplated as dielectric materials in their present form.

TABLE 1 DEPOSITION DIELECTRIC MATERIAL METHOD CONSTANT (k) REFERENCE Fluorinated silicon oxide PE-CVD; 3.3–3.5 U.S. Pat. No. 6,278,174 (SiOF) HDP-CVD Hydrogen SOD 2.0–2.5 U.S Pat. Nos. 4,756,977; 5,370,903; and Silsesquioxane (HSQ) 5,486,564; International Patent Publication WO 00/40637; E. S. Moyer et al., “Ultra Low k Silsesquioxane Based Resins”, Concepts and Needs for Low Dielectric Constant <0.15 μm Interconnect Materials: Now and the Next Millennium, Sponsored by the American Chemical Society, pages 128– 146 (Nov. 14–17, 1999) Methyl Silsesquioxane SOD 2.4–2.7 U.S. Pat. No. 6,143,855 (MSQ) Polyorganosilicon SOD 2.5–2.6 U.S. Pat. No. 6,225,238 Fluorinated Amorphous HDP-CVD 2.3 U.S. Pat. No. 5,900,290 Carbon (a-C:F) Benzocyclobutene (BCB) SOD 2.4–2.7 U.S. Pat. No. 5,225,586 Polyarylene Ether (PAE) SOD 2.4 U.S. Pat. Nos. 5,986,045; 5,874,516; and 5,658,994 Parylene (N and F) CVD 2.4 U.S. Pat. No. 5,268,202 Polyphenylenes SOD 2.6 U.S. Pat. Nos. 5,965,679 and 6,288,188B1; and Waeterloos et al., “Integration Feasibility of Porous SiLK Semiconductor Dielectric”, Proc. Of the 2001 International Interconnect Tech. Conf., pp. 253–254 (2001). Thermosettable SOD 2.3 International Patent Publication WO benzocyclobutenes, 00/31183 polyarylenes, thermosettable perfluoroethylene monomer Poly(phenylquinoxaline), SOD 2.3–3.0 U.S. Pat. Nos. 5,776,990; 5,895,263; organic polysilica 6,107,357; and 6,342,454; and US Patent Publication 2001/0040294 Organic polysilica SOD Not reported U.S. Pat. No. 6,271,273 Organic and inorganic SOD 2.0–2.5 U.S. Pat. No. 6,156,812 Materials Organic and inorganic SOD 2.0–2.3 U.S. Pat. No. 6,171,687 Materials Organic materials SOD Not reported U.S. Pat. No. 6,172,128 Organic SOD 2.12 U.S. Pat. No. 6,214,746 Organosilsesquioxane CVD, SOD <3.9 WO 01/29052 Fluorosilsesquioxane CVD, SOD <3.9 WO 01/29141

Unfortunately, numerous organic SOD systems under development with a dielectric constant between 2.0 and 3.5 suffer from certain drawbacks in terms of mechanical and thermal properties as described above; therefore a need exists in the industry to develop improved processing and performance for dielectric films in this dielectric constant range. In addition, industry demands materials having demonstrated low dielectric constant extendibility, i.e. capable of being reduced to an even lower dielectric constant, e.g., from 2.7 to 2.5 to 2.2 to 2.0 and below.

Reichert and Mathias describe compounds and monomers that comprise adamantane molecules, which are in the class of cage-based molecules and are taught to be useful as diamond substitutes. (Polym, Prepr. (Am. Chem. Soc., Div. Polym. Chem.), 1993, Vol. 34 (1), pp. 495–6; Polym, Prepr. (Am. Chem. Soc., Div. Polym. Chem.), 1992, Vol. 33 (2), pp. 144–5; Chem. Mater., 1993, Vol. 5 (1), pp. 4–5; Macromolecules, 1994, Vol. 27 (24), pp. 7030–7034; Macromolecules, 1994, Vol. 27 (24), pp. 7015–7023; Polym, Prepr. (Am. Chem. Soc., Div. Polym. Chem.), 1995, Vol. 36 (1), pp. 741–742; 205^(th) ACS National Meeting, Conference Program, 1993, pp. 312; Macromolecules, 1994, Vol. 27 (24), pp. 7024–9; Macromolecules, 1992, Vol. 25 (9), pp. 2294–306; Macromolecules, 1991, Vol. 24 (18), pp. 5232–3; Veronica R. Reichert, PhD Dissertation, 1994, Vol. 55–06B; ACS Symp. Ser.: Step-Growth Polymers for High-Performance Materials, 1996, Vol. 624, pp. 197–207; Macromolecules, 2000, Vol. 33 (10), pp. 3855–3859; Polym, Prepr. (Am. Chem. Soc., Div. Polym. Chem.), 1999, Vol. 40 (2), pp. 620–621; Polym, Prepr. (Am. Chem. Soc., Div. Polym. Chem.), 1999, Vol. 40 (2), pp. 577–78; Macromolecules, 1997, Vol. 30 (19), pp. 5970–5975; J. Polym. Sci, Part A: Polymer Chemistry, 1997, Vol. 35 (9), pp. 1743–1751; Polym, Prepr. (Am. Chem. Soc., Div. Polym. Chem.), 1996, Vol. 37 (2), pp. 243–244; Polym, Prepr. (Am. Chem. Soc., Div. Polym. Chem.), 1996, Vol. 37 (1), pp. 551–552; J. Polym. Sci., Part A: Polymer Chemistry, 1996, Vol. 34 (3), pp. 397–402; Polym, Prepr. (Am. Chem. Soc., Div. Polym. Chem.), 1995, Vol. 36 (2), pp. 140–141; Polym, Prepr. (Am. Chem. Soc., Div. Polym. Chem.), 1992, Vol. 33 (2), pp. 146–147; J. Appl. Polym. Sci., 1998, Vol. 68 (3), pp. 475–482). The adamantane-based compounds and monomers described by Reichert and Mathias are preferably used to form polymers with adamantane molecules at the core of a thermoset. The compounds disclosed by Reichert and Mathias in their studies, however, comprise only one isomer of the adamantane-based compound by design choice. Structure A shows this symmetrical para- isomer 1,3,5,7-tetrakis[4′-(phenylethynyl)phenyl]adamantane:

Structure A

In other words, Reichert and Mathias in their individual and joint work contemplated a useful polymer comprising only one isomer form of the target adamantane-based monomer. A significant problem exists, however, when forming and processing polymers from the single isomer form (symmetrical “all-para” isomer) 1,3,5,7-tetrakis[4′-(phenylethynyl)phenyl]adamantane of the adamantane-based monomer. According to the Reichert dissertation (supra) and Macromolecules, vol. 27, (pp. 7015–7034) (supra), the symmetrical all-para isomer 1,3,5,7-tetrakis[4′-(phenylethynyl)phenyl]adamantane “was found to be soluble enough in chloroform that a ¹H NMR spectrum could be obtained. However, acquisition times were found to be impractical for obtaining a solution ¹³C NMR spectrum.” indicating that the all para isomer has low solubility. Thus, the Reichert symmetrical “all-para” isomer 1,3,5,7-tetrakis[4′-(phenylethynyl)phenyl]adamantane is insoluble in standard organic solvents and therefore, would not be useful in any application requiring solubility or solvent-based processing, such as flow coating, spin coating, or dip coating.

In our commonly assigned pending patent application PCT/US01/22204 filed Oct. 17, 2001 (claiming the benefit of our commonly assigned pending patent applications U.S. Ser. No. 09/545,058 filed Apr. 7, 2000; U.S. Ser. No. 09/618,945 filed Jul. 19, 2000; U.S. Ser. No. 09/897,936 filed Jul. 5, 2001; and U.S. Ser. No. 09/902,924 filed Jul. 10, 2001; and International Publication WO 01/78110 published Oct. 18, 2001), we discovered a composition comprising an isomeric thermosetting monomer or dimer mixture, wherein the mixture comprises at least one monomer or dimer having the structure correspondingly

wherein Z is selected from cage compound and silicon atom; R′₁, R′₂, R′₃, R′₄, R′₅, and R′₆ are independently selected from aryl, branched aryl, and arylene ether; at least one of the aryl, the branched aryl, and the arylene ether has an ethynyl group; and R′₇ is aryl or substituted aryl. We also disclose methods for formation of these thermosetting mixtures. This novel isomeric thermosetting monomer or dimer mixture is useful as a dielectric material in microelectronics applications and soluble in many solvents such as cyclohexanone. These desirable properties make this isomeric thermosetting monomer or dimer mixture ideal for film formation at thicknesses of about 0.1 μm to about 1.0 μm.

We filed a patent application Serial No. 60/384,304 on even date herewith that claims a porous version of the preceding isomeric mixture.

Our International Patent Publication WO 01/78110 published Oct. 18, 2001 teaches in its background section that methods for introducing nanosized voids include physical blending or chemical grafting of thermostable or thermolabile portions. This publication's invention is that nanosized voids may be introduced into dielectric materials by using cage structures such as adamantane or diamantane to achieve low dielectric constant material and defines low dielectric constant materials as having a dielectric constant of less than 3.0. However, this publication does not report any dielectric constant for its examples.

International Patent Publication WO 00/31183 teaches in its background section that although known porous thermoplastic materials had acceptable dielectric constants, the pores tended to collapse during subsequent high temperature processing and thus, the art teaches away from adding porosity to the cage structure that introduced nanosized voids in International Patent Publication WO 01/78110 published Oct. 18, 2001. In addition, U.S. Pat. Nos. 5,776,990; 5,895,263; 6,107,357; and 6,342,454 and U.S. Publication 2001/0040294 teach that although dielectric constants of 2.3–2.4 had been achieved at porosity levels less than about 20%, the pore content could not be further increased without comprising the small domain sizes and/or the non-interconnectivity of the pore structure. Similarly, U.S. Pat. Nos. 6,271,273; 6,156,812; 6,171,687; and 6,172,128 teach that the amount of the thermally labile monomer unit is limited to amounts less than about 30% by volume because if more than about 30% by volume of the thermally labile monomer is used, the resulting dielectric material has cylindrical or lamellar domains, instead of pores or voids, which lead to interconnected or collapsed structures upon removal, i.e., heating to degrade the thermally labile monomer units.

Although various methods are known in the art to lower the dielectric constant of a material, these methods have disadvantages. Thus, there is still a need in the semiconductor industry to a) provide improved compositions and methods to lower the dielectric constant of dielectric layers; b) provide dielectric materials with improved properties, such as thermal stability, glass transition temperature (T_(g)), modulus, and hardness; c) produce thermosetting compounds and dielectric materials that are capable of being solvated and spun-on to a wafer or layered material; and d) provide materials with demonstrated extendibility.

The present invention advantageously provides demonstrated extendibility so that semiconductor device manufacturers can use the present compositions for numerous generations of microchips.

SUMMARY OF THE INVENTION

In response to the need in the art and proceeding contrary to the wisdom in the art, we developed a composition comprising:

(a) dielectric material; and

(b) porogen comprising at least two fused aromatic rings wherein each of the fused aromatic rings has at least one alkyl substituent thereon and a bond exists between at least two of the alkyl substituents on adjacent aromatic rings.

We have also discovered a composition comprising a cage structure having a dielectric constant of less than 2.7.

We also discovered a composition comprising:

(a) thermosetting component comprising: (1) optionally monomer of Formula I

and (2) at least one oligomer or polymer of Formula II

where E is a cage compound; each Q is the same or different and selected from aryl, branched aryl, and substituted aryl wherein the substituents include hydrogen, halogen, alkyl, aryl, substituted aryl, heteroaryl, aryl ether, alkenyl, alkynyl, alkoxyl, hydroxyalkyl, hydroxyaryl, hydroxyalkenyl, hydroxyalkynyl, hydroxyl, or carboxyl; G is aryl or substituted aryl where substituents include halogen and alkyl; h is from 0 to 10; i is from 0 to 10; j is from 0 to 10; and w is 0 or 1; and

(b) porogen.

The present invention also includes a method of using the above composition. In one method, the steps comprise: decomposing the porogen; and volatilizing the decomposed porogen whereby the dielectric constant of the dielectric material is lowered. In another method, the steps comprise: decomposing the porogen; and volatilizing the decomposed porogen whereby pores form in the dielectric material.

We have also developed a composition comprising:

(a) compound having at least bifunctionality wherein the bifunctionality may be the same or different and at least one of the first functionality and the second functionality is selected from the group consisting of Si containing groups; N containing groups; C bonded to 0 containing groups; hydroxyl groups; and C double bonded to C containing groups; and

(b) porogen comprising at least two fused aromatic rings wherein each of the fused aromatic rings has at least one alkyl substituent thereon and a bond exists between at least two of the alkyl substituents on adjacent aromatic rings.

BRIEF DESCRIPTION OF THE DRAWINGS

FIGS. 1A through 1F illustrate how to make adamantane based compositions useful as the thermosetting component in the present compositions.

FIG. 2 illustrates one method for making diamantane based compositions useful as the thermosetting component in the present compositions.

FIGS. 3A through 3F illustrate another method for making diamantane based compositions useful as the thermosetting component in the present compositions.

FIG. 4 shows scanning electron microscopy pictures for the cross section of the film of Inventive Examples 44–47.

FIG. 5 shows scanning electron microscopy pictures for the surface of the film of Inventive Examples 44–47.

FIG. 6 shows Thermal Desorption Mass Spectroscopy plots for Inventive Examples 46–49.

DETAILED DESCRIPTION OF THE INVENTION

We filed a patent application 10/158,548 on even date now U.S. Pat. No. 6,740,685 herewith that claims a composition of a thermosetting component and a porogen that bonds to the thermosetting component.

Dielectric Material:

Known dielectric materials such as inorganic, organic, or organic and inorganic hybrid materials may be used with the porogens set forth below. Examples include phenylethynylated-aromatic monomer or oligomer; fluorinated or non-fluorinated poly(arylene ethers) such as taught by commonly assigned U.S. Pat. Nos. 5,986,045; 6,124,421; 6,291,628 and 6,303,733; bisbenzocyclobutene; and organosiloxanes such as taught by commonly assigned pending U.S. patent application Ser. No. 10/078,919 filed Feb. 19, 2002.

The phrases “cage structure”, “cage molecule”, and “cage compound” as used herein are intended to be used interchangeably and refer to a molecule having at least eight atoms arranged such that at least one bridge covalently connects two or more atoms of a ring system. In other words, a cage structure, cage molecule, or cage compound comprises a plurality of rings formed by covalently bound atoms, wherein the structure, molecule, or compound defines a volume, such that a point located within the volume cannot leave the volume without passing through the ring. The bridge and/or the ring system may comprise one or more heteroatoms, and may contain aromatic groups, partially cyclic or acyclic saturated hydrocarbon groups, or cyclic or acyclic unsaturated hydrocarbon groups. Further contemplated cage structures include fullerenes, and crown ethers having at least one bridge. For example, an adamantane or diamantane is considered a cage structure, while a naphthalene or an aromatic spirocompound are not considered a cage structure under the scope of this definition, because a naphthalene or an aromatic spirocompound do not have one, or more than one bridge and thus, do not fall within the description of the cage compound above. Cage compounds are preferably adamantane and diamantane and more preferably adamantane.

The phrase “bridgehead carbon” as used herein refers to any cage structure carbon bound to three other carbons. Thus, for example, adamantane has four bridgehead carbons while diamantane has eight bridgehead carbons.

Preferred dielectric material is thermosetting component disclosed and claimed in our commonly assigned pending patent application 60/347,195 filed Jan. 8, 2002 and 60/384,303 filed on even date herewith, which are incorporated herein by reference in their entireties.

Preferably, the thermosetting component (a) comprises: (1) adamantane monomer of Formula III

and (2) adamantane oligomer or polymer of Formula IV

or (1) diamantane monomer of Formula V

and (2) diamantane oligomer or polymer of Formula VI

wherein h is from 0 to 10; i is from 0 to 10; j is from 0 to 10; each R₁ in Formulae III, IV, V, and VI is the same or different and selected from hydrogen, halogen, alkyl, aryl, substituted aryl, heteroaryl, aryl ether, alkenyl, alkynyl, alkoxyl, hydroxyalkyl, hydroxyaryl, hydroxyalkenyl, hydroxyalkynyl, hydroxyl, or carboxyl; and each Y in Formulae III, IV, V, and VI is the same or different and selected from hydrogen, alkyl, aryl, substituted aryl, or halogen.

Formulae II, IV, and VI represent random or irregular structures in that any one of the units h, i, and j may or may not repeat numerous times before another unit is present. Thus, the sequence of units in Formulae II, IV, and VI above is random or irregular.

In the one embodiment, preferably the thermosetting component comprises adamantane monomer of Formula III above and at least one adamantane oligomer or polymer of Formula IV above where at least one of h, i, and j is at least 1. Preferably, the thermosetting component comprises diamantane monomer of Formula V above and at least one diamantane oligomer or polymer of Formula VI above where at least one of h, i, and j is at least 1.

Preferably, the thermosetting component comprises adamantane monomer of Formula III above and adamantane oligomer or polymer of Formula VII below.

Preferably, the thermosetting component comprises diamantane monomer of Formula V above and diamantane oligomer or polymer of Formula VIII below.

Preferably, the thermosetting component comprises adamantane monomer of Formula III above and adamantane dimer of Formula IX below.

Preferably, the thermosetting component comprises diamantane monomer of Formula V above and diamantane dimer of Formula X below.

Preferably, the thermosetting component comprises adamantane monomer of Formula III above and adamantane trimer of Formula XI below.

Preferably, the thermosetting component comprises diamantane monomer of Formula V above and diamantane trimer of Formula XII below.

Preferably, the thermosetting component comprises adamantane monomer of Formula III above, adamantane dimer of Formula IX above, and at least one adamantane oligomer or polymer of Formula IV above where at least one of h, i, and j is at least 1. Preferably, the thermosetting component comprises diamantane monomer of Formula IV above, diamantane dimer of Formula X above, and at least one diamantane oligomer or polymer of Formula VI above where at least one of h, i, and j is at least 1.

Preferably, the thermosetting component comprises adamantane monomer of Formula II above, adamantane dimer of Formula IX above, adamantane trimer of Formula XI above, and at least one adamantane oligomer or polymer of Formula IV above where at least one of i and j is at least 1. Preferably, the thermosetting component comprises diamantane monomer of Formula V above, diamantane dimer of Formula X above, diamantane trimer of Formula XII above, and at least one diamantane oligomer or polymer of Formula VI above where at least one of i and j is at least 1.

The thermosetting component comprises adamantane monomer of Formula III that is a tetrasubstituted adamantane or a diamantane monomer of Formula V that is a tetrasubstituted diamantane. The preferred monomer is the adamantane monomer of Formula III. The adamantane framework carries a substituted aryl radical in each of positions 1, 3, 5, and 7. The compound with the Formula IV is an oligomer or polymer, linked via unsubstituted and/or substituted aryl units, of the adamantane monomer of Formula III. The compound with the Formula VI is an oligomer or polymer, linked via unsubstituted and/or substituted aryl units, of the diamantane monomer of Formula V. Generally, h, i, and j are whole numbers from 0 to 10, preferably 0 to 5, and more preferably 0 to 2. The simplest adamantane oligomer is thus the dimer (h is 0, i is 0, and j is 0 in Formula IV) as shown in Formula IX above, in which two adamantane frameworks are linked via an unsubstituted or substituted aryl unit. The simplest diamantane oligomer is thus the dimer (h is 0, i is 0, and j is 0 in Formula VI) as shown in Formula X above, in which two diamantane frameworks are linked via an unsubstituted or substituted aryl unit.

In another embodiment, preferably the present thermosetting component comprises at least one adamantane oligomer or polymer of Formula IV above where h is from 0 to 10, i is from 0 to 10, and j is from 0 to 10. Preferably, the present thermosetting component comprises at least one diamantane oligomer or polymer of Formula VI above where h is from 0 to 10, i is from 0 to 10, and j is from 0 to 10.

Preferably, the present thermosetting component comprises at least one adamantane oligomer or polymer of Formula IV above where h is 0 or 1, i is 0, and j is 0. This adamantane structure is shown as Formula VII above.

Preferably, the present thermosetting component comprises at least one diamantane oligomer or polymer of Formula VI above where h is 0 or 1, i is 0, and j is 0. This diamantane structure is shown as Formula VIII above.

Preferably, the thermosetting component comprises at least one adamantane oligomer or polymer of Formula IV above where h is 0, i is 0, and j is 0. This adamantane dimer is shown as Formula IX above.

Preferably, the thermosetting component comprises at least one diamantane oligomer or polymer of Formula VI above where h is 0, i is 0, and j is 0. This diamantane dimer is shown as Formula X above.

Preferably, the thermosetting component comprises at least one adamantane oligomer or polymer of Formula IV above where h is 1, i is 0, and j is 0. This adamantane trimer is as shown in Formula XI above.

Preferably, the thermosetting component (a) comprises at least one diamantane oligomer or polymer of Formula VI above where h is 1, i is 0, and j is 0. This diamantane trimer is as shown in Formula XII above.

Preferably, the thermosetting component comprises a mixture of at least one adamantane oligomer or polymer of Formula IV above where h is 2, i is 0, and j is 0 (linear oligomer or polymer) and h is 0, i is 1, and j is 0 (branched oligomer or polymer). Thus, this composition comprises a mixture of an adamantane linear tetramer as shown in Formula XIII below

and adamantane branched tetramer as shown Formula XIV below

Preferably, the thermosetting component comprises at least one diamantane oligomer or polymer of Formula VI above where h is 2, i is 0, and j is 0 (linear oligomer or polymer) and h is 0, i is 1, and j is 0 (branched oligomer or polymer). Thus, the present composition comprises diamantane linear tetramer as shown in Formula XV below

and diamantane branched tetramer as shown Formula XVI below

Preferably, the thermosetting component comprises adamantane dimer of Formula IX above and adamantane trimer of Formula XI above. Preferably, the thermosetting component comprises diamantane dimer of Formula X above and diamantane trimer of Formula XII above.

Preferably, the thermosetting component comprises adamantane dimer of Formula IX above and at least one adamantane oligomer or polymer of Formula IV above where h is 0, i is at least 1, and j is 0. Preferably, the thermosetting component comprises diamantane dimer of Formula X above and at least one diamantane oligomer or polymer of Formula VI above where h is 0, i is at least 1, and j is 0.

In both embodiments, for Formulae I and II above, preferred Q groups include aryl and aryl substituted with alkenyl and alkynyl groups and more preferred a groups include (phenylethynyl)phenyl, phenylethynyl(phenylethynyl)phenyl, and (phenylethynyl)phenylphenyl moiety. Preferred aryls for G include phenyl, biphenyl, and terphenyl. The more preferred G group is phenyl.

The individual radicals R₁ of the substituted ethynyl radical on the phenyl ring attached to the adamantane or diamantane ring of the type R₁≡C— are in each case the same or different in Formulae III, IV, V, VI, VII, VIII, IX, X, XI, XII, XIII, XIV, XV, and XVI above. R₁ is selected from hydrogen, halogen, alkyl, aryl, substituted aryl, heteroaryl, aryl ether, alkenyl, alkynyl, alkoxyl, hydroxyalkyl, hydroxyaryl, hydroxyalkenyl, hydroxyalkynyl, hydroxyl, or carboxyl. Each R₁ may be unbranched or branched and unsubstituted or substituted and the substituents may be unbranched or branched. It is preferred that the radicals alkyl, alkenyl, alkynyl, alkoxyl, hydroxyalkyl, hydroxyalkenyl, and hydroxyalkynyl contain from about 2 to about 10 carbon atoms and the radicals aryl, aryl ether, and hydroxyaryl contain from about 6 to about 18 carbon atoms. If R₁ stands for aryl, R₁ is preferably phenyl. Preferably, at least two of the R₁C≡C groups on the phenyl groups are two different isomers. Examples of at least two different isomers include meta-, para-, and ortho- isomers. Preferably, the at least two different isomers are meta- and para- isomers. In the preferred monomer, 1,3,5,7-tetrakis[3′/4′-phenylethynyl)phenyl]adamantane (shown in FIG. 1D), five isomers form: (1) para-, para-, para-, para-; (2) para-, para-, para-, meta-; (3) para-, para-, meta-, meta-; (4) para-, meta-, meta-, meta-; and (5) meta-, meta-, meta-, meta-.

Each Y of the phenyl rings in the Formulae III, IV, V, VI, VII, VIII, IX, X, XI, XII, XIII, XIV, XV, and XVI above is in each case the same or different and selected from hydrogen, alkyl, aryl, substituted aryl, or halogen. When Y is aryl, examples of aryl groups include phenyl or biphenyl. Y is selected from preferably hydrogen, phenyl, and biphenyl and more preferably hydrogen. Preferably, at least one of the phenyl groups between two bridgehead carbons of adamantane or diamantane exists as at least two different isomers. Examples of at least two different isomers include meta-, para-, and ortho- isomers. Preferably, the at least two isomers are meta- and para- isomers. In the most preferred dimer 1,3/4-bis{1′,3′,5′-tris[3″/4″-(phenylethynyl)phenyl]adamant-7′-yl}benzene (shown in FIG. 1F), 14 isomers form as follows. Preferably, the phenyl group located between the two bridgehead carbons of the adamantane exists as meta- and para- isomers. For each of the two preceding isomers, seven isomers of the R₁C≡C groups on the phenyl groups exist as follows: (1) para-, para-, para-, para-, para-, para-; (2) para-, para-, para-, para-, para-, meta-; (3) para-, para-, para-, para-, meta-, meta-, (4) para-, para-, para-, meta-, meta-, meta-; (5) para-, para-, meta-, meta-, meta-, meta-; (6) para-, meta-, meta-, meta-, meta-, meta-, and (7) meta-, meta-, meta-, meta-, meta-, meta-.

In addition to the branched adamantane structure of Formula XIV above, it should be understood that Formula IV above when h is 0, i is 0, and j is 1 represents further branching as shown in Formula XVII below. It should be understood that branching may occur beyond that of the Formula XVII structure because further branching of the pending adamantane units of the Formula XVII structure may also occur.

In addition to the branched diamantane structure of Formula XVI above, it should be understood that Formula VI above when h is 0, i is 0, and j is 1 represents further branching as shown in Formula XVIII below. It should be understood that branching may occur beyond that of the Formula XVIII structure because further branching of the pending diamantane units of the Formula XVIII structure may also occur.

In thermosetting component, the monomer and oligomer or polymer contents are determined by the gel permeation chromatography techniques set forth below in the Analytical Test Methods section. The present composition comprises the adamantane or diamantane monomer in a quantity of about 30 to about 70 area-%, more preferably about 40 to about 60 area-% and even more preferably about 45 to about 55 area-% and the oligomer or polymer in a quantity of about 70 to about 30 area-%, more preferably about 60 to about 40 area-%, and even more preferably about 55 to about 45 area-%. Most preferably, the present composition comprises the monomer (1) in a quantity of approximately 50 area-% and the oligomer or polymer (2) in a quantity of approximately 50 area-%.

The Analytical Test Methods section sets forth two Gel Permeation Chromatography Methods. Both provide similar results. One skilled in the art may elect to use the second method in that it yields additional detail on the dimer and trimer.

In general, the quantity ratio of the adamantane or diamantane monomer (1) to oligomer or polymer (2) can be set in a desired manner, e.g. by altering the molar ratio of the starting components during the preparation of the composition according to the invention, by adjusting reaction conditions, and by altering the ratio of nonsolvent to solvent during precipitation/isolation steps.

A preferred process for preparing the thermosetting component (a) comprises the following steps.

In step (A), adamantane or diamantane is reacted with halogeno benzene compound of Formula XIX

where W is halogen, to form a mixture which if adamantane is used, comprises at least one monomer of Formula XX

and at least one oligomer or polymer of Formula XXI where h is from 0 to 10, i is from 0 to 10, and j is from 0 to 10

or if diamantane is used, comprises at least one monomer of Formula XXII

and at least one oligomer or polymer of Formula XXIII where h is from 0 to 10, i is from 0 to 10, and j is from 0 to 10

It should be understood to those skilled in the art that reaction may occur on diamantane at bridgehead carbons other than those indicated in Formulae XXII and XXIII above.

In step (B), the mixture resulting from step (A) is reacted with terminal alkyne of the formula R₁C≡CH. Preferably, the present process forms compositions of Formulae III and IV or V and VI above.

In step (A), adamantane or diamantane is reacted with halogeno benzene compound with the Formula XIX. In addition to the halogen radical W and the previously described radical Y, the halogeno benzene compound can also contain further substituents.

The halogeno benzene compound is preferably selected from bromobenzene, dibromobenzene, and iodobenzene. Bromobenzene and/or dibromobenzene are preferred, bromobenzene being even more preferred.

The reaction of adamantane or diamantane with the halogeno benzene compound (step (A)) takes place preferably through Friedel-Crafts reaction in the presence of a Lewis acid catalyst. Although all customary Lewis acid catalysts may be used, it is preferred that the Lewis acid catalyst contains at least one compound selected from aluminum(III) chloride (AlCl₃), aluminum(III) bromide (AlBr₃), and aluminum (III) iodide (AlI₃). Aluminum(III) chloride (AlCl₃) is most preferred. Despite the greater Lewis acidity of aluminum(III) bromide, its use is generally less preferred, because it has a low sublimation point of only 90° C. and is thus much more difficult to handle on an industrial scale than e.g. aluminum(III) chloride.

In a further preferred version, the Friedel-Crafts reaction is carried out in the presence of a second catalyst component. The second catalyst component preferably contains at least one compound selected from tertiary halogen alkane with 4 to 20 carbon atoms, tertiary alkanol with 4 to 20 carbon atoms, secondary and tertiary olefin with 4 to 20 carbon atoms and tertiary halogen alkyl aryl compound. In particular, the second catalyst component contains at least one compound selected from 2-bromo-2-methylpropane (tert.-butyl bromide), 2-chloro-2-methylpropane (tert.-butyl chloride), 2-methyl-2-propanol (tert.-butyl alcohol), isobutene, 2-bromopropane, and tert.-butylbromobenzene, with 2-bromo-2-methylpropane (tert.-butyl bromide) being most preferred. Overall, compounds whose alkyl groups include 5 or more carbon atoms are less suitable, as solid constituents precipitate out of the reaction solution at the end of the reaction.

It is most preferred that the Lewis acid catalyst is aluminum(III) chloride (AlCl₃) and the second catalyst component is 2-bromo-2-methylpropane (tert.-butyl bromide) or tert.-butylbromobenzene.

The preferable procedure for carrying out the Friedel-Crafts reaction is that adamantane or diamantane, halogeno benzene compound (e.g. bromobenzene), and Lewis acid catalyst (e.g. aluminium chloride) are mixed and heated at a temperature of 30° C. to 50° C., preferably 35° C. to 45° C. and in particular 40° C. At temperatures lower than 30° C., the reaction is not completed, i.e. a higher proportion of tri-substituted adamantane forms for example. In principle it is conceivable to use even higher temperatures than those given above (e.g. 60° C.), but this leads in an undesirable manner to a higher proportion of non-halogenated aromatic material (e.g. benzene) in the reaction mixture of step (A). The second component of the catalyst system, say tert.-butyl bromide, is then added to the above reaction solution generally over a period of 5 to 10 hours, preferably 6 to 7 hours and after the addition has ended, mixed into the reaction mixture in the temperature range named above customarily for a further 5 to 10 hours, preferably 7 hours.

Surprisingly, in addition to the monomeric tetraphenylated compound, e.g. 1,3,5,7-tetrakis(3′/4′-bromophenyl)adamantane, oligomers or polymers thereof were also found in the mixture obtained after step (A). It was wholly unexpected that the quantity ratio of adamantane monomer of Formula XX to adamantane oligomer or polymer of Formula XXI or diamantane monomer of Formula XXII to diamantane oligomer or polymer of Formula XXIII was controllable through the quantities of adamantane or diamantane, halogeno benzene compound (e.g. bromobenzene), and second catalyst component (e.g. tert.-butyl bromide) used. The molar ratio of adamantane or diamantane to halogeno benzene compound to second catalyst component in the reaction mixture of step (A) is preferably 1:(5–15):(2–10) and even more preferably 1:(8–12):(4–8).

In the compounds with the Formulae XX, XXI, XXII, and XXIII, the position of the halogen substituent W is undefined. Preferably, the mixtures comprise meta- and para-isomers which, unlike all para-isomers, advantageously produce improved solubility and good film properties. In the reaction mixture of step (A), in addition to monomers and oligomers or polymers, starting components and by-products, such as not wholly phenylated adamantanes, can also occur.

The mixture resulting from step (A) is optionally worked up using methods known to those skilled in the art. For example, it may be necessary to remove non-reacted halogen phenyl compound, say bromobenzene, from the mixture in order to obtain a product, usable for further reaction, with a high proportion of compounds of Formulae XX, XXI, XXII, and XXIII. Any solvent or solvent mixture which is miscible with the halogeno benzene compound, say bromobenzene, and is suitable for the precipitation of the compounds of Formulae XX, XXI, XXII, and XXIII may be used for the isolation of such a product. It is preferred to introduce the mixture resulting from step (A) into a nonpolar solvent or solvent mixture, e.g. by dropping in, with preference being given to the use of aliphatic hydrocarbons with 7 to 20 carbon atoms or mixtures thereof and in particular at least one component selected from heptane fraction (boiling point 93–99° C.), octane fraction (boiling point 98–110° C.) and alkane mixture currently commercially available from Honeywell International Inc. under the tradename Spezial Benzin 80–110° C. (petroleum ether with boiling point of 80–110° C.). Spezial Benzin 80–110° C. (petroleum ether with boiling point of 80–110° C.) is most preferred. The weight ratio of organic mixture to nonpolar solvent is preferably about 1:2 to about 1:20, more preferably about 1:5 to about 1:13, and even more preferably about 1:7 to about 1:11. Alternatively, a polar solvent or solvent mixture (e.g. methanol or ethanol) can be used for the working-up of the mixture obtained after step (A), but it is less preferred, as the product mixture then precipitates out as a rubbery composition.

We have found that the peak ratio of monomer resulting from step (A) above to its dimer and trimer and oligomer in the reaction mixture shifts dramatically if the step (A) mixture is precipitated into certain solvents. This discovery advantageously allows one skilled in the art to adjust process conditions in order to achieve a targeted ratio of monomer to dimer and trimer and oligomer. To reduce this ratio, preferably, a solvent is used in which the monomer and oligomer or polymer have different solubilities.

Preferred solvents for achieving this monomer to dimer and trimer ratio shift include Spezial Benzin 80–110° C. (petroleum ether with boiling point of 80° C.–110C), ligroine (boiling point 90–110° C.), and heptane (boiling point 98° C.). The more preferred solvent is Spezial Benzin. More specifically, to achieve a shift from about 3:1 monomer:dimer+trimer+oligomer to about 1:1, the step (A) mixture is precipitated into Spezial Benzin or to attain a shift from about 3:1 monomer:dimer+trimer+oligomer to about 1.7–2.0:1.0, the step (A) reaction mixture is precipitated into ligroine and heptane. We know that these substantial changes in peak distribution at precipitation are explained by the loss of monomer in the precipitation filtrates: ⅔ loss in Spezial Benzin and ≧⅓ loss in ligroine and heptane, which correspond to monomer yield losses of 50 and 25–33%. In order for the ratio monomer:dimer+trimer+oligomer 3:1 to remain unchanged, the step (A) reaction mixture is precipitated into methanol where no yield losses are observed. This is corroborated by determination of yield losses of the filtrates and GPC analysis of the filtrates.

Like the synthesis described by Ortiz, the Friedel-Crafts reaction which is carried out according to a preferred version in step (A) of the present process starts direct from adamantane which is coupled with the halogeno benzene compound. Compared with previous syntheses of e.g. 1,3,5,7-tetrakis(3′/4′-bromophenyl)adamantane by Reichert et al., the present process is particularly advantageous because it is no longer necessary to produce tetrabrominated adamantanes first, which saves a reaction step. Also, less unwanted benzene forms.

It is known to those skilled in the art that the halogen radical W in the compounds of Formulae XX, XXI, XXII, and XXIII above can also be introduced, apart from a direct reaction of adamantane with halogen phenyl compound (e.g. with the help of a Friedel-Crafts reaction), by a multi-stage synthesis, for example, by coupling adamantane with a phenyl compound (i.e. without halogen radical W) followed by introduction of the radical W say through addition with W₂ (e.g. Br₂) although this is not preferred.

In step (B) of the preferred process, the (optionally worked-up) mixture obtained after step (A) is reacted with terminal alkyne of the formula R₁C≡CH where R₁ is as previously defined.

In the formula R₁C≡CH, R₁ is identical with the previously described radical R₁ of the adamantane product of Formulae III and IV and the diamantane product of Formulae V and VI. Accordingly it is most preferred to use ethynyl benzene (phenylacetylene) as terminal alkyne for the reaction in step (B).

In order, in step (B), to couple the terminal alkyne to the halogeno benzene radicals located at the adamantane system, all conventional coupling methods suitable for this purpose may be used, as described for example in Diederich, F., and Stang, P. J., (Eds.) “Metal-Catalyzed Cross-Coupling Reactions”, Wiley-VCH 1998 and March, J., “Advanced Organic Chemistry”, 4th Edition, John Wiley & Sons 1992, pages 717/718.

When Y on the phenyl groups is attached to two cage structure bridgehead carbons in Formula XXI above or in Formula XXIII above, Y may react with phenylacetylene to generate terminal alkyne groups.

In a preferred version of the process according to the invention, the reaction of the (optionally worked-up) mixture obtained after step (A) with terminal alkyne is carried out in the presence of a catalyst system as used in the so-called Sonogashira coupling (cf. Sonogashira; Tohda; Hagihara; Tetrahedron Lett. 1975, page 4467). It is even more preferred to use a catalyst system which in each case contains at least one palladium-triarylphosphine complex with the formula [Ar₃P]₂PdX₂ (where Ar=aryl and X=halogen), a copper halide (e.g. CuI), a base (e.g. a trialkylamine), a triarylphosphine and a co-solvent. According to the invention, this preferred catalyst system can equally well consist of the named components. The co-solvent preferably contains at least one component selected from toluene, xylene, chlorobenzene, N,N-dimethylformamide and 1-methyl-2-pyrrolidone (N-methylpyrrolidone (NMP)). A catalyst system which contains the components bis(triphenylphosphine)palladium(II)dichloride (i.e. [Ph₃P]2PdCl₂), triphenylphosphine (i.e. [Ph₃P]), copper(I)-iodide, triethylamine and toluene as co-solvent is most preferred.

The preferred procedure for the reaction of the mixture obtained from step (A) (and optionally worked-up) with terminal alkyne is that the mixture is first mixed with the base (e.g. triethylamine) and the co-solvent (e.g. toluene) and this mixture is stirred for some minutes at room temperature. The palladium-triphenylphosphine complex (e.g. Pd(PPh₃)₂Cl₂), triphenylphosphine (PPh₃) and copper halide (e.g. copper(I)-iodide) are then added, and this mixture is heated in a temperature range of 50° C. to 90° C. (more preferably 80° C. to 85° C.). Terminal alkyne is then added in the named temperature range within 1 to 20 hours (more preferably 3 hours). After the ending of the addition, the mixture is heated for at least 5 to 20 hours (more preferably 12 hours) at a temperature of 75° C. to 85° C. (more preferably 80° C.). Solvent is then added to the reaction solution and distilled off under reduced pressure. Preferably, after filtration, the reaction solution is then cooled to a temperature of 20° C. to 30° C. (more preferably 25° C.). Finally, the reaction mixture of step (B), in particular for the removal of metal traces (e.g. Pd), is worked up with conventional methods which are known to those skilled in the art.

The peak ratio of monomer resulting from step (B) above to its dimer and trimer and oligomer in the reaction mixture shifts if the step (B) mixture is precipitated into certain solvents.

Surprisingly, it transpired that the reaction sequence starting direct from adamantane leads to an oligomeric or polymeric content in the reaction product of step (A) which can be controlled via the use ratio of adamantane, halogeno benzene compound and the second catalyst component, say tert.-butyl bromide. In corresponding manner, the benzene content in the reaction mixture of step (A) is also successfully regulated via this use ratio, which, because of the toxicity of benzene in industrial-scale syntheses, is of great importance. The oligomeric or polymeric content permits the same secondary chemistry as the monomer (e.g. 1,3,5,7-tetrakis(3′/4′-bromophenyl)adamantane, i.e. the oligomer or polymer is just as accessible as the monomer for the reaction with the terminal alkyne in step (B)).

In one embodiment, the thermosetting component and porogen are combined. The amount of thermosetting component used is about 50 to about 90 weight percent while the amount of porogen used is about 10 to about 50 weight percent. The thermosetting component and porogen may or may not react together. Preferably, an adhesion promoter is then added.

Adhesion Promoter:

The phrase “adhesion promoter” as used herein means any component that when added to thermosetting component, improves the adhesion thereof to substrates compared with thermosetting component alone.

The phrase “compound having at least bifunctionality” as used herein means any compound having at least two functional groups capable of interacting or reacting, or forming bonds as follows. The functional groups may react in numerous ways including addition reactions, nucleophilic and electrophilic substitutions or eliminations, radical reactions, etc. Further alternative reactions may also include the formation of non-covalent bonds, such as Van der Waals, electrostatic bonds, ionic bonds, and hydrogen bonds.

In one embodiment, the adhesion promoter and porogen are combined. Based on a composition comprising adhesion promoter, porogen, and thermosetting compound, the amount of adhesion promoter used is about 3 to about 18 weight percent while the amount of porogen used is about 10 to about 50 weight percent. The adhesion promoter and porogen may or may not react together. Preferably, a thermosetting component is then added in an amount of about 32 to about 87 weight percent.

We have found that the adhesion promoter advantageously improves compatibility between the porogen and the thermosetting component. Although not wishing to be bound by theory, we believe that the adhesion promoter acts as an emulsifier so that a homogeneous system is formed.

Adhesion promoter is disclosed in our commonly assigned pending patent application 60/350,187 filed Jan. 15, 2002 which is incorporated herein by reference in its entirety.

In the adhesion promoter, preferably at least one of the first functionality and the second functionality is selected from Si containing groups; N containing groups; C bonded to O containing groups; hydroxyl groups; and C double bonded to C containing groups. Preferably, the Si containing groups are selected from Si—H, Si—O, and Si—N; the N containing groups are selected from such as C—NH₂ or other secondary and tertiary amines, imines, amides, and imides; the C bonded to O containing groups are selected from ═CO, carbonyl groups such as ketones and aldehydes, esters, —COOH, alkoxyls having 1 to 5 carbon atoms, ethers, glycidyl ethers; and epoxies; the hydroxyl group is phenol; and the C double bonded to C containing groups are selected from allyl and vinyl groups. For semiconductor applications, the more preferred functional groups include the Si containing groups; C bonded to O containing groups; hydroxyl groups; and vinyl groups.

An example of a preferred adhesion promoter having Si containing groups is silanes of the Formula XXIV: (R₂)_(k)(R₃)_(l)Si(R₄)_(m)(R₅)_(n) wherein R₂, R₃, R₄, and R₅ each independently represents hydrogen, hydroxyl, unsaturated or saturated alkyl, substituted or unsubstituted alkyl where the substituent is amino or epoxy, saturated or unsaturated alkoxyl, unsaturated or saturated carboxylic acid radical, or aryl; at least two of R₂, R₃, R₄, and R₅ represent hydrogen, hydroxyl, saturated or unsaturated alkoxyl, unsaturated alkyl, or unsaturated carboxylic acid radical; and k+l+m+n≦4. Examples include vinylsilanes such as H₂C═CHSi(CH₃)₂H and H₂C═CHSi(R₆)₃ where R₆ is CH₃O, C₂H₅O, AcO, H₂C═CH, or H₂C═C(CH₃)O—, or vinylphenylmethylsilane; allylsilanes of the formula H₂C═CHCH₂—Si(OC₂H₅)₃ and H₂C═CHCH₂—Si(H)(OCH₃)₂; glycidoxypropylsilanes such as (3-glycidoxypropyl)methyldiethoxysilane and (3-glycidoxypropyl)trimethoxysilane; methacryloxypropylsilanes of the formula H₂C═(CH₃)COO(CH₂)₃-Si(OR₇)₃ where R₇ is an alkyl, preferably methyl or ethyl; aminopropylsilane derivatives including H₂N(CH₂)₃Si(OCH₂CH₃)₃, H₂N(CH₂)₃Si(OH)₃, or H₂N(CH₂)₃OC (CH₃)₂CH═CHSi(OCH₃)₃. The aforementioned silanes are commercially available from Gelest.

An example of a preferred adhesion promoter having C bonded to O containing groups is glycidyl ethers including but not limited to 1,1,1-tris(hydroxyphenyl)ethane tri-glycidyl ether which is commercially available from TriQuest.

An example of a preferred adhesion promoter having C bonded to O containing groups is esters of unsaturated carboxylic acids containing at least one carboxylic acid group. Examples include trifunctional methacrylate ester, trifunctional acrylate ester, trimethylolpropane triacrylate, dipentaerythritol pentaacrylate, and glycidyl methacrylate. The foregoing are all commercially available from Sartomer.

An example of a preferred adhesion promoter having vinyl groups is vinyl cyclic pyridine oligomers or polymers wherein the cyclic group is pyridine, aromatic, or heteroaromatic. Useful examples include but not limited to 2-vinylpyridine and 4-vinylpyridine, commercially available from Reilly; vinyl aromatics; and vinyl heteroaromatics including but not limited to vinyl quinoline, vinyl carbazole, vinylimidazole, and vinyl oxazole.

An example of a preferred adhesion promoter having Si containing groups is the polycarbosilane disclosed in commonly assigned copending allowed U.S. patent application Ser. No. 09/471,299 filed Dec. 23, 1999 incorporated herein by reference in its entirety. The polycarbosilane is of the Formula XXV:

in which R₈, R₁₄, and R₁₇ each independently represents substituted or unsubsalltituted alkylene, cycloalkylene, vinylene, allylene, or arylene; R₉, R₁₀, R₁₁, R₁₀, R₁₅, and R₁₆ each independently represents hydrogen atom or organo group comprising alkyl, alkylene, vinyl, cycloalkyl, allyl, or aryl and may be linear or branched; R₁₃ represents organosilicon, silanyl, siloxyl, or organo group; and p, q, r, and s satisfy the conditions of [4≦p+q+r+s≦100,000], and q and r and s may collectively or independently be zero. The organo groups may contain up to 18 carbon atoms but generally contain from about 1 to about 10 carbon atoms. Useful alkyl groups include —CH₂— and —(CH₂)_(t)— where t>1.

Preferred polycarbosilanes of the present invention include dihydrido polycarbosilanes in which R₈ is a substituted or unsubstituted alkylene or phenyl, R₉ group is a hydrogen atom and there are no appendent radicals in the polycarbosilane chain; that is, q, r, and s are all zero. Another preferred group of polycarbosilanes are those in which the R₉, R₁₀, R₁₁, R₁₂, R₁₅, and R₁₆ groups of Formula XXV are substituted or unsubstituted alkenyl groups having from 2 to 10 carbon atoms. The alkenyl group may be ethenyl, propenyl, allyl, butenyl or any other unsaturated organic backbone radical having up to 10 carbon atoms. The alkenyl group may be dienyl in nature and includes unsaturated alkenyl radicals appended or substituted on an otherwise alkyl or unsaturated organic polymer backbone. Examples of these preferred polycarbosilanes include dihydrido or alkenyl substituted polycarbosilanes such as polydihydridocarbosilane, polyallylhydrididocarbosilane and random copolymers of polydihydridocarbosilane and polyallylhydridocarbosilane.

In the more preferred polycarbosilanes, the R₉ group of Formula XXV is a hydrogen atom and R₈ is methylene and the appendent radicals q, r, and s are zero. Other preferred polycarbosilane compounds of the invention are polycarbosilanes of Formula XXV in which R₉ and R₁₅ are hydrogen, R₈ and R₁₇ are methylene, and R₁₆ is an alkenyl, and appendent radicals q and r are zero. The polycarbosilanes may be prepared from well known prior art processes or provided by manufacturers of polycarbosilane compositions. In the most preferred polycarbosilanes, the R₉ group of Formula XXV is a hydrogen atom; R₈ is —CH₂—; q, r, and s are zero and p is from 5 to 25. These most preferred polycarbosilanes may be obtained from Starfire Systems, Inc. Specific examples of these most preferred polycarbosilanes follow:

Weight Average Peak Molecular Molecular Weight Weight Polycarbosilane (Mw) Polydispersity (Mp) 1   400–1,400   2–2.5 330–500 2   330 1.14 320 3 (with 10% allyl 10,000–14,000 10.4–16   1160  groups) 4 (with 75% allyl 2,400 3.7  410 groups)

As can be observed in Formula XXV, the polycarbosilanes utilized in the subject invention may contain oxidized radicals in the form of siloxyl groups when r>0. Accordingly, R₁₃ represents organosilicon, silanyl, siloxyl, or organo group when r>0. It is to be appreciated that the oxidized versions of the polycarbosilanes (r>0) operate very effectively in, and are well within the purview of the present invention. As is equally apparent, r can be zero independently of p, q, and s the only conditions being that the radicals p, q, r, and s of the Formula XXV polycarbosilanes must satisfy the conditions of [4<p+q+r+s<100,000], and q and r can collectively or independently be zero.

The polycarbosilane may be produced from starting materials that are presently commercially available from many manufacturers and by using conventional polymerization processes. As an example of synthesis of the polycarbosilanes, the starting materials may be produced from common organo silane compounds or from polysilane as a starting material by heating an admixture of polysilane with polyborosiloxane in an inert atmosphere to thereby produce the corresponding polymer or by heating an admixture of polysilane with a low molecular weight carbosilane in an inert atmosphere to thereby produce the corresponding polymer or by heating an admixture of polysilane with a low molecular carbosilane in an inert atmosphere and in the presence of a catalyst such as polyborodiphenylsiloxane to thereby produce the corresponding polymer. Polycarbosilanes may also be synthesized by Grignard Reaction reported in U.S. Pat. No. 5,153,295 hereby incorporated by reference.

An example of a preferred adhesion promoter having hydroxyl groups is phenol-formaldehyde resins or oligomers of the Formula XXVI: —[R₁₈C₆H₂(OH)(R₁₉)]_(u)—where R₁₈ is substituted or unsubstituted alkylene, cycloalkylene, vinyl, allyl, or aryl; R₁₉ is alkyl, alkylene, vinylene, cycloalkylene, allylene, or aryl; and u=3–100. Examples of useful alkyl groups include —CH₂— and —(CH₂)_(v)—where v>1. A particularly useful phenol-formaldehyde resin oligomer has a molecular weight of 1500 and is commercially available from Schenectady International Inc.

The present adhesion promoter is preferably added in small, effective amounts from about 0.5% to up to 20% based on the weight of the present thermosetting composition and amounts up to about 5.0% by weight of the composition are generally more preferred.

By combining the adhesion promoter with the thermosetting component and subjecting the composition to thermal or a high energy source, the resulting compositions have superior adhesion characteristics throughout the entire polymer so as to ensure affinity to any contacted surface of the coating. The present adhesion promoters also improve striation control, viscosity, and film uniformity. Visual inspection confirms the presence of improved striation control.

The present compositions may also comprise additional components such as additional adhesion promoters, antifoam agents, detergents, flame retardants, pigments, plasticizers, stabilizers, and surfactants.

Porogen:

The term “pore” as used herein includes void and cells in a material and any other term meaning space occupied by gas in the material. Appropriate gases include relatively pure gases and mixtures thereof. Air, which is predominantly a mixture of N₂ and O₂, is commonly distributed in the pores but pure gases such as nitrogen, helium, argon, CO₂, or CO are also contemplated. Pores are typically spherical but may alternatively or additionally include tubular, lamellar, discoidal, voids having other shapes, or a combination of the preceding shapes and may be open or closed. The term “porogen” as used herein means a decomposable material that is radiation, thermally, chemically, or moisture decomposable, degradable, depolymerizable, or otherwise capable of breaking down and includes solid, liquid, or gaseous material. The decomposed porogen is removable from or can volatilize or diffuse through a partially or fully cross-linked matrix to create pores in a subsequently fully cured matrix and thus, lower the matrix's dielectric constant and includes sacrificial polymers. Supercritical materials such as CO₂ may be used to remove porogen and decomposed porogen fragments. Preferably, for a thermally decomposable porogen, the porogen comprises a material having a decomposition temperature less than the glass transition temperature (Tg) of a dielectric material combined with it and greater than the curing temperature of the dielectric material combined with it. Thus, the dielectric material and porogen are different materials. Preferably, the present novel porogens have a degradation or decomposition temperature of about 350° C. or greater. Preferably, the degraded or decomposed porogens volatilize at a temperature greater than the cure temperature of the material with which the porogen is combined and less than the Tg of said material. Preferably, the degraded or decomposed porogens volatilize at a temperature of about 280° C. or greater.

Although International Patent Publication WO 00/31183 teaches that a porogen may be added to thermosettable benzocyclobutene, polyarylene, or thermosettable perfluoroethylene monomer to increase porosity thereof and thus, lower the dielectric constant of that resin, the reference teaches that a porogen that is known to function well with a first matrix system will not necessarily function well with another matrix system.

Porogens comprising at least two fused aromatic rings wherein each of the fused aromatic rings has at least one alkyl substituent thereon and a bond exists between at least two of the alkyl substituents on adjacent aromatic rings may be used in the present invention. Preferred porogens include unfunctionalized polyacenaphthylene homopolymer, functionalized polyacenaphthylene homopolymer, the polyacenaphthylene copolymers described below, poly(2-vinylnaphthalene), and vinyl anthracene, and blends with each other. Other useful porogens include adamantane, diamantane, fullerene, and polynorbornene. Each of these porogens may be blended with each other or other porogen materials such as polycaprolactone, polystyrene, and polyester. Useful blends include unfunctionalized polyacenaphthylene homopolymer and polycaprolactone. The more preferred porogens are unfunctionalized polyacenaphthylene homopolymer, functionalized polyacenaphthylene homopolymer, polyacenaphthylene copolymer, and polynorbornene.

Useful polyacenaphthylene homopolymers may have weight average molecular weights ranging from preferably about 300 to about 20,000; more preferably about 300 to about 10,000; and most preferably about 1000 to about 7,000 and may be polymerized from acenaphthylene using different initiators such as 2,2′-azobisisobutyronitrile (AIBN); di-tert-butyl azodicarboxylate; di-isopropyl azodicarboxylate; di-ethyl azodicarboxylate; di-benzyl azodicarboxylate; di-phenyl azodicarboxylate; 1,1′-azobis(cyclohexanecarbonitrile); benzoyl peroxide (BPO); t-butyl peroxide; and boron trifluoride diethyl etherate. The polyacenaphthylene homopolymer may have functional end groups such as triple bonds or double bonds to the chain end or cationic polymerization quenched with a double or triple bond alcohol such as allyl alcohol; propargyl alcohol; butynol; butenol; or hydroxyethylmethacrylate.

European Patent Publication 315453 teaches that silica and certain metal oxides may react with carbon to form volatile sub oxides and gaseous carbon oxide to form pores and teaches that sources of carbon include any suitable organic polymer including polyacenaphthylene. However, the reference does not teach or suggest that polyacenaphthylene is a porogen useful in non-metallic materials or in reducing the dielectric constant of a matrix.

Useful polyacenaphthylene copolymers may be linear polymers, star polymers, or hyperbranched. The comonomer may have a bulky side group that will result in copolymer conformation that is similar to that of polyacenaphthylene homopolymer or a nonbulky side group that will result in copolymer conformation that is dissimilar to that of polyacenaphthylene homopolymer. Comonomers having a bulky side group include vinyl pivalate; tert-butyl acrylate; styrene; α-methylstyrene; tert-butylstyrene; 2-vinylnaphthalene; 5-vinyl-2-norbornene; vinyl cyclohexane; vinyl cyclopentane; 9-vinylanthracene; 4-vinylbiphenyl; tetraphenylbutadiene; stilbene; tert-butylstilbene; and indene; and preferably, vinyl pivalate. Hydridopolycarbosilane may be used as an additional co-monomer or copolymer component with acenaphthylene and at least one of the preceding comonomers. An example of a useful hydridopolycarbosilane has 10% or 75% allyl groups. Comonomers having a nonbulky side group include vinyl acetate; methyl acrylate; methyl methacrylate; and vinyl ether and preferably, vinyl acetate.

Preferably, the amount of comonomer ranges from about 5 to about 50 mole percent of the copolymer. These copolymers may be made by free radical polymerization using initiator. Useful initiators include preferably 2,2′-azobisisobutyronitrile (AIBN); di-tert-butyl azodicarboxylate; di-isopropyl azodicarboxylate; di-ethyl azodicarboxylate; di-benzyl azodicarboxylate; di-phenyl azodicarboxylate; 1,1′-azobis(cyclohexanecarbonitrile); benzoyl peroxide (BPO); and t-butyl peroxide and more preferably, AIBN. Copolymers may also be made by cationic polymerization using initiator such as boron trifluoride diethyl etherate. Preferably, the copolymers have a molecular weight from about 500 to about 15,000.

Thermal properties of copolymers of acenaphthylene and comonomers are set forth in the following Table 2. In Table 2, BA stands for butyl acrylate; VP stands for vinyl pivalate; VA stands for vinyl acetate; AIBN stands for 2,2′-azobisisobutyronitrile; BF₃ stands for boron trifluoride diethyl etherate; DBADC stands for di-tert-butyl azodicarboxylate; W1 stands for weight loss percentage from room temperature to 250° C.; W2 stands for weight loss percentage at 250° C. for 10 minutes; W3 stands for weight loss percentage from 250° C. to 400° C.; W4 stands for weight loss percentage at 400° C. for one hour; and W5 stands for total weight loss.

TABLE 2 Comonomer Temp. Comonomer Copolymer Initiator % Initiator % Solvent (° C.) Time (hr) W1 W2 W3 W4 W5 Mn Mw BA 1 AIBN 11 1 Xylene 70 24 14.63 1.02 33.14 30.44 79.23 4797 10552  BA 2 AIBN 20 1 Xylene 70 24 1.47 0.98 37.92 35.55 75.92 4343 8103 BA 3 AIBN 30 1 Xylene 70 24 13.41 1.6 36.48 27.55 79.04 4638 7826 BA 4 AIBN 50 1 Xylene 70 24 10.01 2.96 46.92 26.51 86.40 3504 5489 BA 5 BF3 10 3 Xylene 5 2 11.93 0.58 40.06 29.33 81.90 1502 2421 VP 6 AIBN 10 1 Xylene 70 24 16.22 0.41 37.8 34.72 89.15 5442 10007  VP 7 AIBN 16 1 THF 60 12 5.32 0.66 46.55 29.59 82.12 1598 2422 VP 8 AIBN 25 1 Xylene 70 24 4.15 0.37 24.98 47.4 76.90 2657 8621 VP 9 AIBN 30 1 Xylene 70 24 14.7 0.69 33.27 39.54 88.20 5342 9303 VP 10 AIBN 40 1 Xylene 70 24 6.34 0.26 33.69 39.38 76.67 4612 7782 VP 11 AIBN 50 1 Xylene 70 24 14.12 0.32 29.01 37.86 81.31 4037 6405 VP 12 BF3 10 1 Xylene 5 2 0.84 0 55.51 39.38 95.73 2078 3229 VP 13 BF3 10 3 Xylene 5 2 2.26 0.06 47.44 28.93 78.69 1786 2821 VP 14 BF3 25 1 Xylene 5 2 0.17 0 36.99 41.17 78.33 2381 3549 VP 15 BF3 25 3 Xylene 5 2 1.33 0.03 35.28 41.08 77.72 2108 3267 VP 16 BF3 40 1 Xylene 5 2 0.23 0.04 36.46 42.17 78.90 2659 3692 VP 17 BF3 40 3 Xylene 5 2 0.28 0.01 40.23 38.98 79.50 2270 3376 VA 18 AIBN 20 2 Xylene 70 24 16.93 1.346 38.42 21.43 78.13 3404 7193 VA 19 AIBN 40 2 Xylene 70 24 15.45 1.631 31.28 31.64 80.00 3109 6141

Known porogens such as linear polymers, star polymers, crosslinked polymeric nanospheres, block copolymers, and hyperbranched polymers may be used with the novel thermosetting component of Formula I or II described above. Suitable linear polymers are polyethers such as poly(ethylene oxide) and poly(propylene oxide); polyacrylates such as poly(methylmethacrylate); aliphatic polycarbonates such as poly(propylene carbonate) and poly(ethylene carbonate); polyesters; polysulfones; polystyrene (including monomer units selected from halogenated styrene and hydroxy-substituted styrene); poly(α-methylstyrene); polylactides; and other vinyl based polymers. Useful polyester porogens include polycaprolactone; polyethylene terephthalate; poly(oxyadipoyloxy-1,4-phenylene); poly(oxyterephthaloyloxy-1,4-phenylene); poly(oxyadipoyloxy-1,6-hexamethylene); polycarbonate such as poly(hexamethylene carbonate) diol having a molecular weight from about 500 to about 2500; and polyether such as poly(bisphenol A-co-epichlorohydrin) having a molecular weight from about 300 to about 6,500. Suitable crosslinked, insoluble nanospheres (prepared as nanoemulsions) are suitably comprised of polystyrene or poly(methylmethacrylate). Suitable block copolymers are poly(styrene-co-α-methylstyrene), poly(styrene-ethylene oxide), poly(etherlactones), poly(estercarbonates), and poly(lactonelactide). Suitable hyperbranched polymers are hyperbranched polyester, e.g., hyperbranched poly(caprolactone), and polyethers such as polyethylene oxide and polypropylene oxide. Another useful porogen is ethylene glycol-poly(caprolactone). Useful polymer blocks include polyvinylpyridines, hydrogenated polyvinyl aromatics, polyacrylonitriles, polysiloxanes, polycaprolactams, polyurethanes, polydienes such as polybutadienes and polyisoprenes, polyvinyl chlorides, polyacetals, and amine-capped alkylene oxides. Other useful thermoplastic materials include polyisoprenes, polytetrahydrofurans, and polyethyloxazolines.

Pore Generation:

The term “degrade” as used herein refers to the breaking of covalent bonds. Such breaking of bonds may occur in numerous ways including heterolytic and homolytic breakage. The breaking of bonds need not be complete, i.e., not all breakable bonds must be cleaved. Furthermore, the breaking of bonds may occur in some bonds faster than in others. Ester bonds, for example, are generally less stable than amide bonds, and therefore, are cleaved at a faster rate. Breakage of bonds may also result in the release of fragments differing from one another, depending on the chemical composition of the degraded portion.

In the pore generation process, for thermally degradable porogens, thermal energy is applied to the porogen containing material to substantially degrade or decompose the porogen into its starting components or monomers. As used herein, “substantially degrade” preferably means at least 80 weight percent of the porogen degrades or decomposes. For the preferred thermosetting component of Formulae I and II above, the Tg is from about 400° C. to about 450° C. so the present porogens which have a degradation or decomposition temperature of about 350° C. or greater are particularly useful with this thermosetting component. For the preferred polyacenaphthylene based homopolymer or copolymer porogen, we have found by using analytical techniques such as Thermal Desorption Mass Spectroscopy that the porogen degrades, decomposes, or depolymerizes into its starting components of acenaphthylene monomer and comonomer.

Thermal energy is also applied to volatilize the substantially degraded or decomposed porogen out of the thermosetting component matrix. Preferably, the same thermal energy is used for both the degradation and volatilization steps. As the amount of volatilized degraded porogen increases, the resulting porosity of the thermosetting component increases. For the preferred thermosetting components of Formulae I and II above, the Tg is from about 400° C. to about 450° C. so the present substantially degraded porogens which have a volatilization temperature of about 280° C. or greater are particularly useful with the thermosetting component.

Preferably, the cure temperature used for cross-linking the thermosetting component will also substantially degrade the porogen and volatilize it out of the thermosetting matrix. Typical cure temperature and conditions will be described in the Utility section below.

The resulting pores may be uniformly or randomly dispersed throughout the matrix. Preferably, the pores are uniformly dispersed throughout the matrix.

Alternatively, other procedures or conditions which at least partially remove the porogen without adversely affecting the thermosetting component may be used. Preferably, the porogen is substantially removed. Typical removal methods include, but are not limited to, exposure to radiation, such as but not limited to, electromagnetic radiation such as ultraviolet, x-ray, laser, or infrared radiation; mechanical energy such as sonication or physical pressure; or particle radiation such as gamma ray, alpha particles, neutron beam, or electron beam.

Utility:

The term “layer” as used herein includes film and coating.

The term “low dielectric constant polymer” as used herein refers to an organic, organometallic, or inorganic polymer with a dielectric constant of approximately 3.0, or lower. The low dielectric material is typically manufactured in the form of a thin layer having a thickness from 100 to 25,000 Angstroms but also may be used as thick films, blocks, cylinders, spheres etc.

The present composition of thermosetting component, adhesion promoter, and porogen is useful in lowering the dielectric constant of a material. Preferably, the dielectric material has a dielectric constant k of less than or equal to about 3.0 and more preferably, from about 1.9 to 3.0. The dielectric material has a glass transition temperature of preferably at least about 350° C.

Layers of the instant compositions of thermosetting component, adhesion promoter, and porogen may be formed by solution techniques such as spraying, rolling, dipping, spin coating, flow coating, or casting, with spin coating being preferred for microelectronics. Preferably, the present composition is dissolved in a solvent. Suitable solvents for use in such solutions of the present compositions include any suitable pure or mixture of organic, organometallic, or inorganic molecules that are volatized at a desired temperature. Suitable solvents include aprotic solvents, for example, cyclic ketones such as cyclopentanone, cyclohexanone, cycloheptanone, and cyclooctanone; cyclic amides such as N-alkylpyrrolidinone wherein the alkyl has from about 1 to 4 carbon atoms; and N-cyclohexylpyrrolidinone and mixtures thereof. A wide variety of other organic solvents may be used herein insofar as they are able to aid dissolution of the adhesion promoter and at the same time effectively control the viscosity of the resulting solution as a coating solution. Various facilitating measures such as stirring and/or heating may be used to aid in the dissolution. Other suitable solvents include methyethylketone, methylisobutylketone, dibutyl ether, cyclic dimethylpolysiloxanes, butyrolactone, γ-butyrolactone, 2-heptanone, ethyl 3-ethoxypropionate, polyethylene glycol [di]methyl ether, propylene glycol methyl ether acetate (PGMEA), and anisole, and hydrocarbon solvents such as mesitylene, xylenes, benzene, and toluene. Preferred solvent is cyclohexanone. Typically, layer thicknesses are between 0.1 to about 15 microns. As a dielectric interlayer for microelectronics, the layer thickness is generally less than 2 microns.

The present composition may be used in electrical devices and more specifically, as an interlayer dielectric in an interconnect associated with a single integrated circuit (“IC”) chip. An integrated circuit chip typically has on its surface a plurality of layers of the present composition and multiple layers of metal conductors. It may also include regions of the present composition between discrete metal conductors or regions of conductor in the same layer or level of an integrated circuit.

In application of the instant polymers to ICs, a solution of the present composition is applied to a semiconductor wafer using conventional wet coating processes such as, for example, spin coating; other well known coating techniques such as spray coating, flow coating, or dip coating may be employed in specific cases. As an illustration, a cyclohexanone solution of the present composition is spin-coated onto a substrate having electrically conductive components fabricated therein and the coated substrate is then subjected to thermal processing. An exemplary formulation of the instant composition is prepared by dissolving the present composition in cyclohexanone solvent under ambient conditions with strict adherence to a clean-handling protocol to prevent trace metal contamination in any conventional apparatus having a non-metallic lining. The resulting solution comprises based on the total solution weight, from preferably about 2 to about 30 weight percent of thermosetting component, adhesion promoter, and porogen, and about 70 to about 98 weight percent solvent and more preferably about 5 to about 25 weight percent of thermosetting component, adhesion promoter, and porogen, and about 75 to about 95 weight percent solvent.

An illustration of the use of the present invention follows. Application of the instant compositions to form a layer onto planar or topographical surfaces or substrates may be carried out by using any conventional apparatus, preferably a spin coater, because the compositions used herein have a controlled viscosity suitable for such a coater. Evaporation of the solvent by any suitable means, such as simple air drying during spin coating, by exposure to an ambient environment, or by heating on a hot plate up to 350° C., may be employed. The substrate may have on it at least one layer of the present preferred composition of thermosetting component, adhesion promoter, and porogen.

Substrates contemplated herein may comprise any desirable substantially solid material. Particularly desirable substrate layers comprise films, glass, ceramic, plastic, metal or coated metal, or composite material. In preferred embodiments, the substrate comprises a silicon or gallium arsenide die or wafer surface, a packaging surface such as found in a copper, silver, nickel or gold plated leadframe, a copper surface such as found in a circuit board or package interconnect trace, a via-wall or stiffener interface “copper” includes considerations of bare copper and its oxides), a polymer-based packaging or board interface such as found in a polyimide-based flex package, lead or other metal alloy solder ball surface, glass and polymers. Useful substrates include silicon, silicon nitride, silicon oxide, silicon oxycarbide, silicon dioxide, silicon carbide, silicon oxynitride, titanium nitride, tantalum nitride, tungsten nitride, aluminum, copper, tantalum, organosiloxanes, organo silicon glass, and fluorinated silicon glass. In other embodiments, the substrate comprises a material common in the packaging and circuit board industries such as silicon, copper, glass, and polymers. The present compositions may also be used as a dielectric substrate material in microchips, multichip modules, laminated circuit boards, or printed wiring boards. The circuit board made up of the present composition will have mounted on its surface patterns for various electrical conductor circuits. The circuit board may include various reinforcements, such as woven non-conducting fibers or glass cloth. Such circuit boards may be single sided, as well as double sided.

Layers made from the present compositions possess a low dielectric constant, high thermal stability, high mechanical strength, and excellent adhesion to electronic substrate surfaces. Because the adhesion promoter is molecularly dispersed, these layers demonstrate excellent adhesion to all affixed surfaces including underlying substrates and overlaid capping or masking layers, such as SiO₂ and Si₃N₄ capping layers. The use of these layers eliminates the need for an additional process step in the form of at least one primer coating application to achieve adhesion of the film to a substrate and/or overlaid surface.

After application of the present composition to an electronic topographical substrate, the coated structure is subjected to a bake and cure thermal process at increasing temperatures ranging from about 50° C. up to about 450° C. to polymerize the coating. The curing temperature is at least about 300° C. because a lower temperature is insufficient to complete the reaction herein. Generally, it is preferred that curing is carried out at temperatures of from about 375° C. to about 425° C. Curing may be carried out in a conventional curing chamber such as an electric furnace, hot plate, and the like and is generally performed in an inert (non-oxidizing) atmosphere (nitrogen) in the curing chamber. In addition to furnace or hot plate curing, the present compositions may also be cured by exposure to ultraviolet radiation, microwave radiation, or electron beam radiation as taught by commonly assigned patent publication PCT/US96/08678 and U.S. Pat. Nos. 6,042,994; 6,080,526; 6,177,143; and 6,235,353, which are incorporated herein by reference in their entireties. Any non oxidizing or reducing atmospheres (e.g., argon, helium, hydrogen, and nitrogen processing gases) may be used in the practice of the present invention, if they are effective to conduct curing of the present adhesion promoter-modified thermosetting component to achieve the low k dielectric layer herein.

While not to be construed as limiting, it is observed that the processing used to prepare the present low dielectric constant composition results in a homogeneous solution of thermosetting component, adhesion promoter, and porogen. The preferred silane adhesion promoter advantageously serves multiple functions in the low dielectric constant composition. For example, the processing of the present composition enables the preferred polycarbosilane adhesion promoter to interact with both the porogen and the unsaturated structures of thermosetting component. It is believed that the silane portions of the preferred polycarbosilane interact with the porogen and thermosetting component. It is speculated that the polycarbosilane acts as a surfactant or emulsification agent to uniformly disperse the porogen within the thermosetting component in the low dielectric composition. This is critical to producing a composition that gives a homogeneous film (or layer) with uniformly dispersed pores of very small dimension. The silane portion of the polycarbosilane also reacts with the substrate surfaces, thereby creating a chemically bonded adherent interface for the dominant thermosetting monomer precursor. It has been proposed that silylene/silyl radicals being available throughout the composition act as attachment sources to fasten and secure any interface surface of contact by chemical bonding therewith. The interactions between the various components and the reactions of the silane portion may occur during formulation and treatment prior to layer formation. As indicated, the dispersion of silane functionality with the porogen and thermosetting component throughout the composition accounts for the uniform porosity in the resulting layers. The dispersion of the silane functionality also leads to reactive radicals as well as the superb adhesion of the instant layers to both underlying substrate surfaces as well as overlayered surface structures such as cap or masking layers. Crucial to the materials discovered herein are the findings that the preferred Formula XXV polycarbosilane adhesion promoters have a hydrido substituted silicon in the backbone structure of the polycarbosilane. This feature of the polycarbosilane enables it to: (1) mix uniformly with the porogen to form a homogeneous composition, (2) be reactive with thermosetting component; (3) uniformly blend and disperse the porogen within the thermosetting component providing a uniform composition leading to uniform distribution of small pores in the final porous layer, and (4) generate a polycarbosilane-modified thermosetting composition and porous layer that possesses improved adhesion performance.

As indicated earlier, the present adhesion promoter-modified thermosetting component (a) coating may act as an interlayer and be covered by other coatings, such as other dielectric (SiO₂) coatings, SiO₂ modified ceramic oxide layers, silicon containing coatings, silicon carbon containing coatings, silicon nitrogen containing coatings, silicon-nitrogen-carbon containing coatings, diamond like carbon coatings, titanium nitride coatings, tantalum nitride coatings, tungsten nitride coatings, aluminum coatings, copper coatings, tantalum coatings, organosiloxane coatings, organo silicon glass coatings, and fluorinated silicon glass coatings. Such multilayer coatings are taught in U.S. Pat. No. 4,973,526, which is incorporated herein by reference. And, as amply demonstrated, the present polycarbosilane-modified thermosetting component (a) prepared in the instant process may be readily formed as interlined dielectric layers between adjacent conductor paths on fabricated electronic or semiconductor substrates.

Advantageously the present layer has a dielectric constant of less than 2.7, preferably less than 2.5, more preferably less than 2.2, and most preferably less than 2.0.

The present films may be used in dual damascene (such as copper) processing and substractive metal (such as aluminum or aluminum/tungsten) processing for integrated circuit manufacturing. The present compositions may be used as an etch stop, hardmask, air bridge, or passive coating for enveloping a completed wafer. The present composition may be used in a desirable all spin-on stacked film as taught by Michael E. Thomas, “Spin-On Stacked Films for Low k_(eff) Dielectrics”, Solid State Technology (July 2001), incorporated herein in its entirety by reference. The present layers may be used in stacks with other layers comprising organosiloxanes such as taught by commonly assigned U.S. Pat. No. 6,143,855 and pending U.S. Ser. No. 10/078919 filed Feb. 19, 2002; Honeywell International Inc.'s commercially available HOSP® product; nanoporous silica such as taught by commonly assigned U.S. Pat. No. 6,372,666; Honeywell International Inc.'s commercially available NANOGLASS® E product; organosilsesquioxanes taught by commonly assigned WO 01/29052; and fluorosilsesquioxanes taught by commonly assigned WO 01/29141, incorporated herein in their entirety.

Analytical Test Methods:

Proton NMR: A 2–5 mg sample of the material to be analyzed was put into an NMR tube. About 0.7 ml deuterated chloroform was added. The mixture was shaken by hand to dissolve the material. The sample was then analyzed using a Varian 400 MHz NMR.

High Performance Liquid Chromatography (HPLC): A HPLC with a Phenomenex luna Phenyl-Hexyl 250×4.6 mm 5 micron column was used. The column temperature was set at 40° C. Water and acetonitrile were used to improve peak separation.

TIME WATER ACETONITRILE Initial 20%   80% 10 minutes 0% 100% 30 minutes 0% 100% The following experimental conditions were used:

INJECTION VOLUME 10 microliters DETECTION UV at 200 nm STOP TIME 30 minutes POST TIME  5 minutes

The samples were prepared as follows.

For a mixture of the halogenated intermediate such as the mixture of 1,3,5,7-tetrakis(3′/4′-bromophenyl)adamantane and 1,3/4-bis[1′,3′,5′-tris(3″/4″-bromophenyl]adamant-7′-yl]benzene of Preparation 1 below, the reaction mixture (0.5–1 milliliter) was shaken with approximately 4% HCl (several milliliters). The organic layer was shaken with water. An organic layer sample (twenty microliters) was taken and added to acetonitrile (one milliliter).

For a mixture of the final product such as the mixture of 1,3,5,7-tetrakis[3′/4′-(phenylethynyl)phenyl]adamantane and 1,3/4-bis{1′,3′, 5′-tris[3″/4″-(phenylethynyl)phenyl]adamant-7′-yl}benzene of Preparation 1 below, the reaction mixture (0.5 gram) was mixed with chloroform (five milliliters) and 3–5% HCl (5 milliliters) and shaken. The organic layer was washed by water. An organic layer sample (100 microliters) was added to tetrahydrofuran (0.9 milliliter).

Gel Permeation Chromatography (GPC 1): The GPC analysis was done with Waters liquid chromatography system composed from Water 717 plus Autosampler, Waters in-line degasser, Waters 515 HPLC pump, Waters 410 Differential Refractometer (RI detector), and two columns: HP PI gel 5 μ MIXED D. The analysis conditions were:

Mobile Phase Tetrahydrofuran (THF) Column flow (milliliters/min)  1.0 Column temperature (° C.) 40.0 Detection Refractive Index, Polarity positive Analysis run time 25 min Injection quantity (μL) 50 The solid product sample (10 milligrams) was prepared by dissolving in tetrahydrofuran (one milliliter).

Gel Permeation Chromatography (GPC 2): This method may be used to provide additional detail about the dimer and trimer peaks. The following conditions are used:

Analysis Apparatus Shimadzu LC10 Separation Column Plgel 5μ pre-column Plgel 5μ 1000Å, 300 × 7.5 nm Plgel 5μ 500Å, 300 × 7.5 nm Plgel 5μ 100Å, 300 × 7.5 nm Mobile Phase Eluent A: toluene Column Flow (milliliters/minute)  1.0 Column Temperature (° C.) 40 Detection Refractive Index, Polarity Positive Analysis Run Time (minutes) 32 Trial Solution 10 milligrams/milliliter toluene Injection Quantity (μ) 50 To calculate the contents, in other words area-%, the peak area belonging to the monomer or the peak area belonging to the oligomer or polymer is related to the total of all the peak areas in the chromatogram.

Gel Permeation Chromatography (GPC 3): Separation was performed with a Waters 2690 separation module with Waters 996 diode array and Waters 410 differential refractometer detectors. The separation was performed on two PLgel 3 μm Mixed-E 300×7.5 mm columns with chloroform flowing at 1 ml/min. Injection volumes of 25 μl of solutions of about 1 mg/ml concentration were run in duplicate. Good reproducibility was observed.

The column was calibrated with relatively monodisperse polystyrene standards between 20,000 and 500 molecular weight. With the lower molecular weight standards nine distinct components could be resolved corresponding to butyl terminated styrene monomer through oligomers with nine styrenes. The logs of the peak molecular weight of the standards were fit with a third order polynomial of the elution time. The instrumental broadening was evaluated from the ratio of the full width at half maximum to the mean elution time of toluene.

The absorbance for Preparations 1 and 2 below was a maximum at about 284 nm. The chromatograms had similar shapes at absorbance at wavelengths below about 300 nm. The results presented here correspond to 254 nm absorbance. The peaks were identified by the molecular weight of the polystyrene that would be eluting at the same time. These values should not be considered as measurements of molecular weight of the Preparation 1 and 2 oligomers. The sequential elution of higher oligomers, trimers, dimers, oligomers, and incomplete oligomers at increasing times can be quantitated.

Each component was broader than that which would be observed for a monodisperse species. This width was analyzed from the full width in minutes at half maximum of the peak. To roughly account for the instrumental broadening, we calculated width_(corrected)=[width_(observed) ²−width_(instrument) ²]^(1/2) where width_(instrument) is the observed width of toluene corrected by the ratio of the elution times of the peak to that for toluene. The peak width was converted to a molecular weight width through the calibration curve and ratioed to the peak molecular width. Since the molecular weight of styrene oligomers was proportional to the square of their size, the relative molecular weight width can be converted to a relative oligomer size width by dividing by 2. This procedure accounted for the difference in molecular configuration of the two species.

Liquid Chromatography-Mass Spectroscopy (LC-MS): This analysis was performed on a Finnigan/MAT TSQ7000 triple stage quadrupole mass spectrometer system, with an Atmospheric Pressure Ionization (API) interface unit, using a Hewlett-Packard Series 1050 HPLC system as the chromatographic inlet. Both mass spectral ion current and variable single wavelength UV data were acquired for time-intensity chromatograms.

Chromatography was conducted on a Phenomenex Luna 5-micron pheny-hexyl column (250×4.6 mm). Sample auto-injections were generally between 5 and 20 microliters of concentrated solutions, both in tetrahydrofuran and without tetrahydrofuran. The preferred preparation of concentrated sample solutions for analysis was dissolution in tetrahydrofuran, of about 5 milligrams solid product per milliliter, for 10 microliter injections. The mobile phase flow through the column was 1.0 milliliter/minute of acetonitrile/water, initially 70/30 for 1 minute then gradient programmed to 100% acetonitrile at 10 minutes and held until 40 minutes.

Atmospheric Pressure Chemical Ionization (APCI) mass spectra were recorded in both positive and negative ionization, in separate experiments. Positive APCI was more informative of molecular structure for these final products, providing protonated pseudomolecular ions including adducts with acetonitrile matrix. The APCI corona discharge was 5 microamps, about 5 kV for positive ionization, and about 4 kV for negative ionization. The heated capillary line was maintained at 200° C. and the vaporizer cell at 400° C. The ion detection system after quadrupole mass analysis was set at 15 kV conversion dynode and 1500V electron multiplier voltage. Mass spectra were typically recorded at 1.0 second/scan from about m/z 50 to 2000 a.m.u. for negative ionization, and from about m/z 150 a.m.u. up for positive ionization. In separate positive ion experiments, the mass range was scanned up both to 2000 a.m.u. in low mass tune/calibration mode and to 4000 a.m.u. in high mass tune/calibration mode.

Differential Scanning Calorimetry (DSC): DSC measurements were performed using a TA Instruments 2920 Differential Scanning Calorimeter in conjunction with a controller and associated software. A standard DSC cell with temperature ranges from 250° C. to 725° C. (inert atmosphere: 50 ml/min of nitrogen) was used for the analysis. Liquid nitrogen was used as a cooling gas source. A small amount of sample (10–12 mg) was carefully weighed into an Auto DSC aluminum sample pan (Part # 990999-901) using a Mettler Toledo Analytical balance with an accuracy of ±0.0001 grams. Sample was encapsulated by covering the pan with the lid that was previously punctured in the center to allow for outgasing. Sample was heated under nitrogen from 0° C. to 450° C. at a rate of 100° C./minute (cycle 1), then cooled to 0° C. at a rate of 100° C./minute. A second cycle was run immediately from 0° C. to 450° C. at a rate of 100° C./minute (repeat of cycle 1). The cross-linking temperature was determined from the first cycle.

FTIR analysis: FTIR spectra were taken using a Nicolet Magna 550 FTIR spectrometer in transmission mode. Substrate background spectra were taken on uncoated substrates. Film spectra were taken using the substrate as background. Film spectra were then analyzed for change in peak location and intensity.

Dielectric Constant: The dielectric constant was determined by coating a thin film of aluminum on the cured layer and then doing a capacitance-voltage measurement at 1 MHz and calculating the k value based on the layer thickness.

Glass Transition Temperature (Tg): The glass transition temperature of a thin film was determined by measuring the thin film stress as a function of temperature. The thin film stress measurement was performed on a KLA 3220 Flexus. Before the film measurement, the uncoated wafer was annealed at 500° C. for 60 minutes to avoid any errors due to stress relaxation in the wafer itself. The wafer was then deposited with the material to be tested and processed through all required process steps. The wafer was then placed in the stress gauge, which measured the wafer bow as function of temperature. The instrument calculated the stress versus temperature graph, provided that the wafer thickness and the film thickness were known. The result was displayed in graphic form. To determine the Tg value, a horizontal tangent line was drawn (a slope value of zero on the stress vs. temperature graph). Tg value was where the graph and the horizontal tangent line intersect.

It should be reported if the Tg was determined after the first temperature cycle or a subsequent cycle where the maximum temperature was used because the measurement process itself may influence Tg.

Isothermal Gravimetric Analysis (ITGA) Weight Loss: Total weight loss was determined on the TA Instruments 2950 Thermogravimetric Analyzer (TGA) used in conjunction with a TA Instruments thermal analysis controller and associated software. A Platinel II Thermocouple and a Standard Furnace with a temperature range of 25° C. to 1000° C. and heating rate of 0.1° C. to 100° C./min were used. A small amount of sample (7 to 12 mg) was weighed on the TGA's balance (resolution: 0.1 g; accuracy: to ±0.1% and heated on a platinum pan. Samples were heated under nitrogen with a purge rate of 100 ml/min (60 ml/min going to the furnace and 40 ml/min to the balance). Sample was equilibrated under nitrogen at 20° C. for 20 minutes, then temperature was raised to 200° C. at a rate of 10° C./minute and held at 200° C. for 10 minutes. Temperature was then ramped to 425° C. at a rate of 10° C./minute and held at 425° C. for 4 hours. The weight loss at 425° C. for the 4 hour period was calculated.

Shrinkage: Film shrinkage was measured by determining the film thickness before and after the process. Shrinkage was expressed in percent of the original film thickness. Shrinkage was positive if the film thickness decreased. The actual thickness measurements were performed optically using a J. A. Woollam M-88 spectroscopic ellipsometer. A Cauchy model was used to calculate the best fit for Psi and Delta (details on Ellipsometry can be found in e.g. “Spectroscopic Ellipsometry and Reflectometry” by H. G. Thompkins and William A. McGahan, John Wiley and Sons, Inc., 1999).

Refractive Index: The refractive index measurements were performed together with the thickness measurements using a J. A. Woollam M-88 spectroscopic ellipsometer. A Cauchy model was used to calculate the best fit for Psi and Delta. Unless noted otherwise, the refractive index was reported at a wavelenth of 633 nm (details on Ellipsometry can be found in e.g. “Spectroscopic Ellipsometry and Reflectometry” by H. G. Thompkins and William A. McGahan, John Wiley and Sons, Inc., 1999).

Modulus and Hardness: Modulus and hardness were measured using instrumented indentation testing. The measurements were performed using a MTS Nanoindenter XP (MTS Systems Corp., Oak Ridge, Tenn.). Specifically, the continuous stiffness measurement method was used, which enabled the accurate and continuous determination of modulus and hardness rather than measurement of a discrete value from the unloading curves. The system was calibrated using fused silica with a nominal modulus of 72+−3.5 GPa. The modulus for fused silica was obtained from average value between 500 to 1000 nm indentation depth. For the thin films, the modulus and hardness values were obtained from the minimum of the modulus versus depth curve, which is typically between 5 to 15% of the film thickness.

Tape Test: The tape test was performed following the guidelines given in ASTM D3359-95. A grid was scribed into the dielectric layer according to the following. A tape test was performed across the grid marking in the following manner: (1) a piece of adhesive tape, preferably Scotch brand #3 m600-1/2X1296, was placed on the present layer, and pressed down firmly to make good contact; and (2) the tape was then pulled off rapidly and evenly at an angle of 180° to the layer surface. The sample was considered to pass if the layer remained intact on the wafer, or to have failed if part or all of the film pulled up with the tape.

Stud Pull Test: Epoxy-coated studs were attached to the surface of a wafer containing the layers of the present invention. A ceramic backing plate was applied to the back side of the wafer to prevent substrate bending and undue stress concentration at the edges of the stud. The studs were then pulled in a direction normal to the wafer surface by a testing apparatus employing standard pull protocol steps. The stress applied at the point of failure and the interface location were then recorded.

Compatibility with Solvents: Compatibility with solvents was determined by measuring film thickness, refractive index, FTIR spectra, and dielectric constant before and after solvent treatment. For a compatible solvent, no significant change should be observed.

Average Pore Size Diameter: The N₂ isotherms of porous samples was measured on a Micromeretics ASAP 2000 automatic isothermal N₂ sorption instrument using UHP (ultra high purity industrial gas) N₂, with the sample immersed in a sample tube in a liquid N₂ bath at 77° K.

For sample preparation, the material was first deposited on silicon wafers using standard processing conditions. For each sample, three wafers were prepared with a film thickness of approximately 6000 Angstroms. The films were then removed from the wafers by scraping with a razor blade to generate powder samples. These powder samples were pre-dried at 180° C. in an oven before weighing them, carefully pouring the powder into a 10 mm inner diameter sample tube, then degassing at 180° C. at 0.01 Torr for >3 hours.

The adsorption and desorption N₂ sorption was then measured automatically using a 5 second equilibration interval, unless analysis showed that a longer time was required. The time required to measure the isotherm was proportional to the mass of the sample, the pore volume of the sample, the number of data points measured, the equilibration interval, and the P/Po tolerance. (P is actual pressure of the sample in the sample tube. Po is the ambient pressure outside the instrument.) The instrument measures the N₂ isotherm and plots N₂ versus P/Po.

The apparent BET (Brunauer, Emmett, Teller method for multi-layer gas absorption on a solid surface disclosed in S. Brunauer, P. H. Emmett, E. Teller; J. Am. Chem. Soc., 60, 309–319 (1938)) surface area was calculated from the lower P/Po region of the N2 adsorption isotherm using the BET theory, using the linear section of the BET equation that gives an R² fit>0.9999.

The pore volume was calculated from the volume of N₂ adsorbed at the relative pressure P/Po value, usually P/Po{tilde over ( )}0.95, which is in the flat region of the isotherm where condensation is complete, assuming that the density of the adsorbed N₂ is the same as liquid N₂ and that all the pores are filled with condensed N₂ at this P/Po.

The pore size distribution was calculated from the adsorption arm of the N₂ isotherm using the BJH (E. P. Barret, L. G. Joyner, P. P. Halenda; J. Am. Chem. Soc., 73, 373–380 (1951)) pore size distribution from the N2 isotherm using the Kelvin equation) theory. This uses the Kelvin equation, which relates curvature to suppression of vapor pressure, and the Halsey equation, which describes the thickness of the adsorbed N₂ monolayer versus P/Po, to convert the volume of condensed N₂ versus P/Po to the pore volume in a particular range of pore sizes.

The average cylindrical pore diameter D was the diameter of a cylinder that has the same apparent BET surface area Sa (m²/g) and pore volume Vp (cc/g) as the sample, so D (nm)=4000 Vp/Sa.

Thermal Desorption Mass Spectroscopy: Thermal Desorption Mass Spectroscopy (TDMS) is used to measure the thermal stability of a material by analyzing the desorbing species while the material is subjected to a thermal treatment.

The TDMS measurement was performed in a high vacuum system equipped with a wafer heater and a mass spectrometer, which was located close to the front surface of the wafer. The wafer was heated using heating lamps, which heat the wafer from the backside. The wafer temperature was measured by a thermocouple, which was in contact with the front surface of the wafer. Heater lamps and thermocouple were connected to a programmable temperature controller, which allowed several temperature ramp and soak cycles. The mass spectrometer was a Hiden Analytical HAL IV RC RGA 301. Both mass spectrometer and the temperature controller were connected to a computer, which read and recorded the mass spectrometer and the temperature signal versus time.

To perform TDMS analysis, the material was first deposited as a thin film onto an 8 inch wafer using standard processing methods. The wafer was then placed in the TDMS vacuum system and the system was pumped down to a pressure below 1e-7 torr. The temperature ramp was then starting using the temperature controller. The temperature and the mass spectrometer signal were recorded using the computer. For a typical measurement with a ramp rate of about 10 degree C. per minute, one complete mass scan and one temperature measurement are recorded every 20 seconds. The mass spectrum at a given time and temperature at a given time can be analyzed after the measurement is completed.

EXAMPLES

Comparative A:

We measured the dielectric constant of a composition similar to Example 5 of our International Patent Publication WO 01/78110 and the dielectric constant was 2.7.

Comparative B:

Although WO 00/31183 teaches that polybutadiene is useful as a porogen, we tried polybutadiene as a porogen by adding it to a composition similar to Inventive Examples 4–7 in our pending U.S. Ser. 60/350,187 filed Jan. 15, 2002 and learned that regardless of the polybutadiene's molecular weight, the composition's refractive index did not change as shown in Table 3 below and thus, a lower dielectric constant material could not be achieved.

TABLE 3 Adhesion Re- Porogen Promoter fractive Porogen % % Solvent Index Polybutadiene 35 6.7 Xylene 1.629 (Mw 1800) Polybutadiene phenyl 35 6.7 Cyclohexanone 1.623 terminated (Mw 1000) Poly(indene-co- 35 6.7 Cyclohexanone 1.602 coumarone) (Mw 735) Poly(indene-co- 35 6.7 Xylene 1.607 coumarone) (Mw 735) Poly(indene-co- 35 6.7 Cyclohexanone 1.600 coumarone) (Mw 1090) Poly(indene-co- 35 6.7 Xylene 1.595 coumarone) (Mw 1090) Preparations: Preparation 1—Preparation of Thermosetting Component (Referred to Herein as “P1”)

Step (a): Preparation of Mixture of 1,3,5,7-tetrakis(3′/4′-bromophenyl)adamantane (shown in FIG. 1A); 1,3/4-bis[1′,3′,5′-tris(3″/4″-bromophenyl)adamant-7′-yl]benzene (shown in FIG. 1C); and at least 1,3-bis{3′/4′-[1″,3″,5″-tris(3′″/4′″-bromophenyl)adamant-7″-yl]phenyl}-5,7-bis(3″″/4″″-bromophenyl)adamantane (shown in FIG. 1C) (collectively “P1 Step (a) Product”)

A first reaction vessel was loaded with adamantane (200 grams), bromobenzene (1550 milliliters), and aluminum trichloride (50 grams). The reaction mixture was heated to 40° C. by a thermostatted water bath. Tert-butyl bromide (1206 grams) was added slowly over a period of 4–6 hours to the reaction mixture. The reaction mixture at 40° C. was stirred overnight.

A second reaction vessel was loaded with 1000 milliliters of aqueous hydrogen chloride (5% w/w). The contents of the first reaction vessel were gradually discharged into the second reaction vessel while maintaining the reaction mixture at 25–35° C. by an external ice bath. An organic phase (dark brown lower phase) was separated and washed with water (1000 milliliters). About 1700 milliliters of the organic phase remained.

A third reaction vessel was loaded with 20.4 liters of petroleum ether (mainly isooctane with a boiling range of 80° C.–110° C.). The contents of the second reaction vessel were slowly added over a period of one hour to the third reaction vessel. The resulting mixture was stirred for at least one hour. The precipitate was filtered off and the filter cake was washed twice with 300 milliliters per wash of the aforementioned petroleum ether. The washed filter cake was dried overnight at 45° C. at 40 mbar. The P1 Step (a) Product yield was 407 grams dry weight. This reaction is shown in FIGS. 1A through 1C as follows. FIG. 1A shows the resulting monomer. FIG. 1B shows the resulting generic dimer and higher products while FIG. 1C shows the resulting specific dimer and trimer covered by the FIG. 1B structure.

Analytical techniques including GPC, HPLC, and NMR were used to identify the product. GPC analysis showed: 1,3,5,7-tetrakis(3′/4′-bromophenyl)adamantane (shown in FIG. 1A) had a peak molecular weight of 430; 1,3/4-bis[1′,3′,5′-tris(3″/4″-bromophenyl)adamant-7′-yl]benzene (shown in FIG. 1C) had a peak molecular weight of 820; 1,3-bis{3′/4′-[1″,3″,5″-tris(3′″/4′″-bromophenyl)adamant-7″-yl]phenyl}-5,7-bis(3″″/4″″-bromophenyl)adamantane (shown in FIG. 1C) had a peak molecular weight of about 1150 (shoulder).

Step (b): Preparation of Mixture of 1,3,5,7-tetrakis[3′,4′-(phenylethynyl)phenyl]adamantane (shown in FIG. 1D); 1,3/4-bis{1′,3′,5′-tris[3″/4″-(phenylethynyl)phenyl]adamant-7′-yl}benzene (shown in FIG. 1F); and at least 1,3-bis{3′/4′-[1″,3″,5″-tris[3′″/4′″-(phenylethynyl)phenyl]adamant-7″-yl]phenyl}-5,7-bis[3″″/4″″-(phenylethynyl)phenyl]adamantane (shown in FIG. 1F) (collectively “P1 Step (b) Product”)

A first reactor under nitrogen was loaded with toluene (1500 milliliters), triethylamine (4000 milliliters), and the P1 Step (a) Product prepared above (1000 grams dry). The mixture was heated to 80° C. and bis-(triphenyl-phosphine)palladium(II)dichloride (i.e., [Ph₃P]₂PdCl₂) (7.5 grams) and tri-phenylphosphine (i.e. [Ph₃P]) (15 grams) were added. After ten minutes, copper(I)iodide (7.5 grams) was added.

Over a period of three hours, a solution of phenylacetylene (750 grams) was added to the first reactor. The reaction mixture at 80° C. was stirred for 12 hours to ensure that the reaction was complete. Toluene (4750 milliliters) was added. The solvent was then distilled off under reduced pressure and a maximum sump temperature and the reaction mixture was cooled down to about 50° C. The triethylammonium bromide (about 1600 milliliters) was filtered off. The filter cake was washed three times with 500 milliliters per wash of toluene. The organic phase was washed with 1750 milliliters of HCl (10 w/w %) and then washed with water (2000 milliliters).

To the washed organic phase, water (1000 milliliters), ethylene diamine tetraacetic acid (EDTA) (100 grams), and dimethylglyoxime (20 grams) were added. About 150 milliliters of NH₄OH (25 w/w %) were added to achieve a pH of 9. The reaction mixture was stirred for one hour. The organic phase was separated and washed with water (1000 milliliters). With a Dean-Stark trap, azeotropic drying occurred until water evolution ceased. Filtering agent dolomite (100 grams) (tradename Tonsil) was added. The mixture was heated to 100° C. for 30 minutes. Dolomite was filtered off with a cloth filter having fine pores and the remainder was washed with toluene (200 milliliters). Silica (100 grams) was added. The reaction mixture was stirred for 30 minutes. The silica was filtered off with a cloth filter having fine pores and the remainder was washed with toluene (200 milliliters). Aqueous NH₃ (20 w/w %), in an amount of 2500 milliliters, and 12.5 g of N-acetylcysteine were added. The phases were separated. The organic phase was washed with 1000 milliliters of HCl (10% w/w) and then washed two times with 1000 milliliters per wash of water. The toluene was distilled off under a reduced pressure of about 120 mbar. The pot temperature did not exceed about 70° C. A dark brown viscous oil (1500–1700 milliliters) remained. To the hot mass in the pot, iso-butyl acetate (2500 milliliters) was added and a dark brown solution formed (4250 milliliters).

A second reactor was loaded with 17000 milliliters of petroleum ether (mainly isooctane with a boiling range of 80° C.–110° C.). The contents of the first reactor were added over a period of one hour to the second reactor and stirred overnight. The precipitate was filtered and washed four times with 500 milliliters per wash of the aforedescribed petroleum ether. The product was dried under reduced pressure for four hours at 45° C. and five hours at 80° C. The P1 Step (B) Product yield was 850–900 grams. This reaction is shown in FIGS. 1D through 1F as follows. FIG. 1D shows the resulting monomer. FIG. 1E shows the resulting generic dimer and higher products while FIG. 1F shows the resulting specific dimer and trimer covered by the FIG. 1F structure.

Analytical techniques including GPC, HPLC, NMR, and FTIR were used to identify the product. GPC analysis showed: 1,3,5,7-tetrakis[3′,4′-(phenylethynyl)phenyl]adamantane (shown in FIG. 1D) had a peak molecular weight of about 900; 1,3/4-bis{1′,3′,5′-tris[3″/4″-(phenylethynyl)phenyl]adamant-7′-yl} benzene (shown in FIG. 1F) had a peak molecular weight of about 1500; 1,3-bis{3′/4′-[1 ″, 3″,5″-tris[3′″/4′″-(phenylethynyl)phenyl]adamant-7″-yl]phenyl}-5,7-bis[3″″/4″″-(phenylethynyl)phenyl]adamantane (shown in FIG. 1F) had a peak molecular weight of about 2100 (shoulder).

The melting point was 164–167° C. From NMR, a multiplet occurred at 6,9–8 ppm 2,8+−0,2H (aromatic part) and 1,7–2,7 ppm 1H+−0,2H (cage portion). From GPC, the ratio of the monomeric and small molecules to oligomeric compounds was 50±5%. FTIR showed the following:

PEAKS IN CENTIMETERS⁻¹ (PEAK INTENSITY) STRUCTURE 3050 (weak) Aromatic C—H 2930 (weak) Aliphatic C—H on adamantane 2200 (very weak) Acetylene 1600 (very strong) Aromatic C═C 1500 (strong) 1450 (medium) 1350 (medium) LC-MS study showed the presence of peaks:

-   -   of main monomeric product m/z 840,     -   of its derivatives, m/z 640, 740, 940; 706, 606, 806; 762, 662,         862; 938, 838, 1038     -   of dimeric products, m/z 1402, 1302, 1502; 1326, 1226, 1426.

The GPC 3 results follow.

Amount Peak Molecular Weight Weight % (Relative to PS) Inc Hi Inc ΔR/R Mnmr Mnmr Dmr Trmr Olgmr Mnmr Mnmr Dmr Trmr Mnmr w/mnmr 49.3 30.9 10.1 9.7 744 1304 1676 0.10 Preparation 2—Preparation of Thermosetting Component (Referred to Herein as “P2”)

Step (a): Preparation of Mixture of 1,3,5,7-tetrakis(3′/4′-bromophenyl)adamantane (shown in FIG. 1A); 1,3/4-bis[1′,3′,5′-tris(3″/4″-bromophenyl)adamant-7′-yl] benzene (shown in FIG. 1C); and at least 1,3-bis{3′/4′-[1″,3″,5″-tris(3′″/4′″-bromophenyl)adamant-7″-yl]phenyl}-5,7-bis(3″″/4″″-bromophenyl)adamantane(shown in FIG. 1C)(collectively “P2 Step (a) Product”)

A first reaction vessel was loaded with 1,4-dibromobenzene (587.4 grams) and aluminum trichloride (27.7 grams). This reaction mixture was heated to 90° C. by a thermostatted water bath and maintained at this temperature for one hour without stirring and for an additional one hour with stirring. The reaction mixture was cooled down to 50° C. Adamantane (113.1 grams) was added to the cooled reaction mixture. Over a period of four hours, t-butyl-bromobenzene (796.3 grams) was added to the reaction mixture. The reaction mixture was stirred for an additional 12 hours.

A second reaction vessel was loaded with HCl (566 milliliters, 10% aqueous w/w). The contents of the first reaction vessel at 50° C. were discharged into the second reaction vessel while maintaining the mixture at 25–35° C. by an external ice bath. The reaction mass was a light brown suspension. The organic phase was a dark brown lower phase and separated from the reaction mixture. The separated organic phase was washed with water (380 milliliters). After this washing, about 800 milliliters of organic phase remained.

A third reaction vessel was loaded with heptane (5600 milliliters). Slowly over a period of one hour, the contents of the second reaction vessel were added to the third reaction vessel. The suspension was stirred for at least four hours and the precipitate was filtered off. The filter cake was washed twice with 300 milliliters per wash of heptane. The P2 Step (a) Product yield was 526.9 grams (wet) and 470.1 grams (dry).

Analytical techniques including GPC, HPLC, and NMR were used to identify the product. GPC analysis showed: 1,3,5,7-tetrakis(3′/4′-bromophenyl)adamantane (shown in FIG. 1A) had a peak molecular weight of about 430; 1,3/4-bis[1′,3′,5′-tris(3″/4″-bromophenyl)adamant-7′-yl] benzene (shown in FIG. 1C) had a peak molecular weight of about 820; 1,3-bis{3′/4′-[1″,3″,5″-tris(3′″/4′″-bromophenyl)adamant-7″-yl]phenyl}-5,7-bis(3″″/4″″-bromophenyl)adamantane (shown in FIG. 1C) had a peak molecular weight of about 1150 (shoulder).

Step (b): Preparation of Mixture of 1,3,5,7-tetrakis[3′,4′-(phenylethynyl)phenyl]adamantane (shown in FIG. 1D); 1,3/4-bis{1′,3′,5′-tris[3″/4″-(phenylethynyl)phenyl]adamant-7′-yl}benzene (shown in FIG. 1F); and at least 1,3-bis{3′/4′-[1 ″, 3″,5″-tris[3 ′″/4′″-(phenylethynl)phenyl]adamant-7″-yl]phenyl}-5,7-bis[3″″/4″″-(phenylethynyl)phenyl]adamantane (shown in FIG. 1F)(collectively “P2 Step (b) Product”)

A first reaction pot under nitrogen was loaded with toluene (698 milliliters), triethylamine (1860 milliliters), and the P2 Step (a) Product prepared above (465 grams dry). The mixture was heated to 80° C. Palladium-triphenylphosphine complex (i.e. [Ph(PPh₃)₂Cl₂)(4.2 grams) was added to the reaction mixture. After waiting ten minutes, triphenylphosphine (i.e., PPh₃)(8.4 grams) was added to the reaction mixture. After waiting another ten mintues, copper(I)-iodide (4.2 grams) was added to the reaction mixture.

Over a period of three hours, a solution of phenylacetylene (348.8 grams) was added to the reaction mixture. The reaction mixture at 80° C. was stirred for 12 hours to ensure that the reaction was complete. Toluene (2209 milliliters) was added to the reaction mixture and then distilled off under reduced pressure and a maximum sump temperature. The reaction mixture was cooled down to about 50° C. and the triethylammonium bromide was filtered off. The filter cake was washed twice with 250 milliliters per wash of toluene. The organic phase was washed with HCl (10 w/w %)(500 milliliters) and water (500 milliliters).

To the organic phase, water (500 milliliters), EDTA (18.6 grams), and dimethylglyoxime (3.7 grams) were added. NH₄OH (25 w/w %)(about 93 milliliters) was added to keep the pH=9. The reaction mixture was stirred for one hour. The organic phase was separated from the insoluble material and the emulsion containing the palladium-complex. The separated organic phase was washed with water (500 milliliters). With a Dean-Stark trap, azeotropic drying of the washed organic phase occurred until water evolution ceased. Filtering agent dolomite (tradename Tonsil)(50 grams) was added and the reaction mixture was heated to 100° C. for 30 minutes. The dolomite was filtered off with a cloth filter having fine pores and the organic material was washed with toluene (200 milliliters). Silica (50 grams) was added and the reaction mixture was stirred for 30 minutes. The silica was filtered off with a cloth filter having fine pores and the organic material was washed with toluene (200 milliliters). Aqueous NH₃ (20% w/w)(250 milliliters) and N-acetylcysteine (12.5 grams) were added. The phases were separated. The organic phase was washed with HCl(10% w/w)(500 milliliters). The organic material was washed twice with 500 milliliters per wash of water. The toluene was distilled off under reduced pressure of about 120 mbar. The pot temperature did not exceed 70° C. A dark brown viscous oil (about 500–700 milliliters) remained. To the hot mass in the pot, iso-butyl acetate (1162 milliliters) was added. A dark brown solution (about 1780 milliliters) formed.

A second reaction pot was loaded with heptane (7120 milliliters). Over a period of one hour, the contents of the first reaction pot were added to the second reaction pot. The precipitate was stirred for at least three hours and filtered off. The product was washed four times with 250 milliliters per wash of heptane. The product was dried under reduced pressure of 40 mbar at 80° C. The P2 Step (b) Product yield was 700 grams wet or 419 grams dry.

Analytical techniques including GPC, HPLC, and NMR were used to identify the product. GPC analysis showed: 1,3,5,7-tetrakis[3′,4′-(phenylethynyl)phenyl]adamantane (shown in FIG. 1D) had a peak molecular weight of about 900; 1,3/4-bis{1′,3′,5′-tris[3″/4″-(phenylethynyl)phenyl]adamant-7′-yl}benzene (shown in FIG. 1F) had a peak molecular weight of about 1500; 1,3-bis{3′/4′-[1″,3″,5″-tris[3′″/4′″-(phenylethynyl)phenyl]adamant-7″-yl]phenyl}-5,7-bis[3″″/4″″-(phenylethynyl)phenyl]adamantane (shown in FIG. 1F) had a peak molecular weight of about 2100 (shoulder).

The melting point was 164–167° C. From NMR, a multiplet occurred at 6,9–8 ppm 2,8+−0,2H (aromatic part) and 1,7–2,7 ppm 1H+−0,2H (cage portion). From GPC, the ratio of the monomeric and small molecules to oligomeric compounds was 50±5%. FTIR showed the following:

PEAKS IN CENTIMETERS⁻¹ (PEAK INTENSITY) STRUCTURE 3050 (weak) Aromatic C—H 2930 (weak) Aliphatic C—H on adamantane 2200 (very weak) Acetylene 1600 (very strong) Aromatic C═C 1500 (strong) 1450 (medium) 1350 (medium) LC-MS study showed the presence of peaks:

-   -   of main monomeric product m/z 840,     -   of its derivatives, m/z 640, 740, 940; 706, 606, 806; 762, 662,         862; 938, 838, 1038     -   of dimeric products, m/z 1402, 1302, 1502; 1326, 1226, 1426.

GPC 3 results follow.

Amount Peak Molecular Weight Weight % (Relative to PS) Inc Hi Inc ΔR/R Mnmr Mnmr Dmr Trmr Olgmr Mnmr Mnmr Dmr Trmr Mnmr 7.7 36.4 26.8 12.3 16.8 546 763 1328 1672 0.14 Preparation 3

Impact of Solvent on ratio of 1,3,5,7-tetrakis[3′,4′-(phenylethynyl)phenyl]adamantane (shown in FIG. 1D) to 1,3/4-bis{1′,3′,5′-tris[3″/4″-phenylethynyl)phenyl]adamant-7′-yl} benzene (shown in FIG. 1F) and at least 1,3-bis{3′/4′-[1″,3″,5″-tris[3 ′″/4′″-(phenylethynyl)phenyl]adamant-7″-yl]phenyl}-5,7-bis[3″″/4″″-(phenylethynyl) phenyl]adamantane (shown in FIG. 1F)

850 milliliters of P1 Step (a) Product was divided into four equal parts, and subjected to precipitation in petroleum ether, ligroine, heptane, and methanol. Each part was precipitated into 2520 ml of the solvent, vacuum filtered (Büchner funnel diam. 185 mm), washed on filter twice by 150 ml of the solvent, then dried in a vacuum oven for two hours at about 20° C., overnight at 40° C., and at 70–80° C. to constant weight.

Precipitation into hydrocarbons resulted in very dispersed light beige powders that dried without complications. Precipitation into methanol gave heavy, brownish granular solid (particles size approximately 1 mm), which formed tar when dried at 20° C. This product was dried further.

Reaction mixtures were analyzed by GPC during the reaction and before precipitation. All filtrates and final solids were analyzed by GPC and the results are in Table 4. In Table 4, PPT stands for precipitation, monomer is 1,3,5,7-tetrakis(3′/4′-bromophenyl)adamantane (shown in FIG. 1A); dimer is 1,3/4-bis[1′,3′,5′-tris(3″/4″-bromophenyl)adamant-7′-yl]benzene (shown in FIG. 1C); and trimer is 1,3-bis{3′/4′-[1″, 3″,5″-tris(3′″/4′″-bromophenyl)adamant-7″-yl]phenyl}-5,7-bis(3″″/4″″-bromophenyl)adamantane (shown in FIG. 1C).

TABLE 4 Peak Ratio [monomer to (dimer + trimer)] before Peak Ratio [monomer to PPT Solvent For PPT (dimer + trimer)] after PPT 75.0:25.0 Petroleum Ether 52.5:47.4 75.0:25.0 Ligroine 64.0:36.0 75.0:25.0 Heptane 66.2:33.8 75.0:25.0 Methanol 75.0:25.0

To summarize these results, the peak ratio of monomer to (dimer+trimer) in the reaction mixture was about 3:1. The product lost in hydrocarbons precipitation filtrates was mostly (>90%) monomer while losses in washing filtrates were negligible. There is no product in methanol precipitation filtrates. The monomer to (dimer+trimer) ratio after precipitation increases (1:1→3:1), and monomer losses in the filtrates decrease (56→0%) in the sequence: petroleum ether, ligroine, heptane, and methanol.

Preparation 4—Preparation of Thermosetting Component

The 1,3/4-bis{1′,3′, 5′-tris[3″/4″-(phenylethynyl)phenyl]adamant-7′-yl}benzene (shown in FIG. 1F) in the Preparation 1 product mixture is separated using preparative liquid chromatography (PLC). PLC is similar to the HPLC method described above but uses larger columns to separate larger quantities of the mixture (from several grams to several hundred grams).

Preparation 5—Preparation of Thermosetting Component

The 1,3-bis{3′/4′-[1″,3″,5″-tris[3′″/4′″-(phenylethynyl)phenyl]adamant-7″-yl]phenyl}-5,7-bis[3″″/4″″-(phenylethynyl)phenyl]adamantane (shown in FIG. 1F) in the Preparation 1 product mixture is separated using preparative liquid chromatography (PLC).

Preparation 6—Preparation of Thermosetting Component

The diamantane monomer of Formula V and oligomer or polymer of diamantane monomer of Formulae VI, VIII, X, XII, XV, XVI, and XVIII are prepared using the following method. As shown in FIG. 2, diamantane is converted using bromine and a Lewis Acid catalyst to brominated diamantane product. The brominated diamantane product is then reacted with bromobenzene in the presence of a Lewis Acid catalyst to form bromophenylated diamantane. The bromophenylated diamantane is then reacted with a terminal alkyne in the presence of a catalyst system as used in the so-called Sonogashira coupling reaction. The product at each step is worked up as described in our pending patent application PCT/US01/22204 filed Oct. 17, 2001.

Preparation 7—Preparation of Thermosetting Component (a)

The diamantane monomer of Formula V and oligomer or polymer of diamantane monomer of Formulae VI, VIII, X, XII, XV, XVI, and XVIII are prepared using the following method. As shown in FIGS. 1A through 1F, diamantane is converted to the bromophenylated compositions of diamantane using similar synthetic procedures as described in Preparations 1 and 2. In FIGS. 1A through 1C, diamantane is reacted with a substituted halogen phenyl compound in the presence of a Lewis Acid catalyst as described in Preparations 1 and 2, and/or a second catalyst component as described in Preparation 2. A mixture of monomers, dimers, trimers, and higher oligomers is obtained after work-up of the reaction mixtures. In FIGS. 1D through 1F, the bromophenylated diamantane mixture is then reacted with a terminal alkyne in the presence of catalyst to produce the alkyne-substituted diamantane compositions of the present invention.

Inventive Example 1 Preparation of Porogen Comprising Copolymer of Acenaphthylene and Vinyl Pivalate

A porogen comprising copolymer of acenaphthylene and vinyl pivalate was made as follows. To a 250-milliliter flask equipped with a magnetic stirrer were added 20 grams of technical grade acenaphthylene (75% pure—corresponds to 0.986 mole of pure acenaphthylene), 3.1579 grams (0.0246 mole) of vinyl pivalate, 0.5673 gram (2.464 millimole) of di-tert-butyl azodicarboxylate and 95 milliliters of xylenes. The mixture was stirred at room temperature for ten minutes until a homogeneous solution was obtained. The reaction solution was then degassed at reduced pressure for five minutes and purged with nitrogen. This process was repeated three times. The reaction mixture was then heated to 140° C. for six hours under nitrogen. The solution was cooled to room temperature and added into 237 milliliters of ethanol dropwise. The mixture was kept stirring at room temperature for another 20 minutes. The precipitate that formed was collected by filtration and dried under vacuum. The resulting copolymer properties are listed as Copolymer 18 in Table 2 above. Other porogens comprising copolymers of acenaphthylene and vinyl pivalate were prepared in a similar manner but varying the comonomer percentage used, initiator type and percentage used, and reaction time and temperature as set forth in Table 2 above.

Inventive Example 2 Preparation of Porogen Comprising Copolymer of Acenaphthylene and Tert-butyl Acrylate

A porogen comprising copolymer of acenaphthylene and tert-butylacrylate was made as follows. To a 250-milliliter flask equipped with a magnetic stirrer were added 20 grams of technical grade acenaphthylene (75% pure—corresponds to 0.0986 mole of pure acenaphthylene), 2.5263 grams (0.01971 mole) of tert-butyl acrylate, 0.3884 gram (2.365 millimole) of 2,2′-azobisisobutyronitrile, and 92 milliliters xylenes. The mixture was stirred at room temperature for 10 minutes until a homogeneous solution was obtained. The reaction solution was then degassed at reduced pressure for 5 minutes and purged with nitrogen. This process was repeated three times. The reaction mixture was then heated to 70° C. for 24 hours under nitrogen. The solution was cooled to room temperature and added into 230 milliliters of ethanol dropwise. The mixture was kept stirring at room temperature for another 20 min. The precipitate that formed was collected by filtration and dried under vacuum. The resulting copolymer properties are listed as Copolymer 2 in Table 2 above. Other porogens comprising copolymers of acenaphthylene and tert-butylacrylate were prepared in a similar manner but varying the comonomer percentage used, initiator type and percentage used, and reaction time and temperature as set forth in Table 2 above.

Inventive Example 3 Preparation of Porogen Comprising Copolymer of Acenaphthylene and Vinyl Acetate

A porogen comprising copolymer of acenaphthylene and vinyl acetate was made as follows. To a 250-milliliter flask equipped with a magnetic stirrer were added 20 grams of technical grade acenaphthylene (75% pure—corresponds to 0.986 mole of pure acenaphthylene), 1.6969 grams (0.01971 mole) of vinyl acetate, 0.3884 gram (2.365 millimole) of 2,2′-azobisisobutyronitrile and 88 milliliters xylenes. The mixture was stirred at room temperature for 10 minutes until a homogeneous solution was obtained. The reaction solution was then degassed at reduced pressure for 5 minutes and purged with nitrogen. This process was repeated three times. The reaction mixture was then heated to 70° C. for 24 hours under nitrogen. The solution was cooled to room temperature and added into 220 milliliters of ethanol dropwise. The mixture was kept stirring at room temperature for another 20 minutes. The precipitate that formed was collected by filtration and dried under vacuum. The resulting copolymer properties are listed as Copolymer 18 in Table 2 above. Another porogen comprising copolymers of acenaphthylene and vinyl acetate was prepared in a similar manner but varying the comonomer percentage used; the resulting copolymer properties are listed as Copolymer 19 in Table 2 above.

Inventive Example 4 Preparation of Porogen Comprising Polyacenaphthylene Homopolymer

A polymer of acenaphthylene was made as follows. To a 250-milliliter flask equipped with a magnetic stirrer were added 30 grams of technical grade acenaphthylene (75% pure—corresponds to 0.148 mole of pure acenaphthylene), 0.3404 gram of di-tert-butyl azodicarboxylate (1.478 millimole) and 121 milliliters xylenes. The mixture was stirred at room temperature for 10 minutes until a homogeneous solution was obtained. The reaction solution was then degassed at reduced pressure for five minutes and purged with nitrogen. This process was repeated three times. The reaction mixture was then heated to 140° C. for six hours under nitrogen. The solution was cooled to room temperature and added into 303 milliliters of ethanol dropwise. The mixture was kept stirring at room temperature for another 20 minutes. The precipitate that formed was collected by filtration and dried under vacuum. The resulting homopolymer properties are listed as Homopolymer 1 in Table 5 below where DBADC stands for di-tert-butyl azodicarboxylate and PDI stands for polydisperseion index (Mw/Mn). Other porogens comprising polyacenaphthylene homopolymer were prepared in a similar manner but varying the initiator type and percentage used and the reaction time and temperature as set forth in Table 5 where below AIBN stands for 2,2′-azobisisobutyronitrile.

TABLE 5 Initiator Homopolymer Type Initiator % Solvent Temp. (C.) Time (hr) Mn Mw PDI 1 DBADC 1% Xylene 140 6 3260 14469  4.44 2 DBADC 2% Xylene 140 6 2712 11299  4.17 3 DBADC 3% Xylene 140 6 3764 14221  3.78 4 DBADC 4% Xylene 140 6 3283 8411 2.56 5 DBADC 6% Xylene 140 6 2541 7559 2.97 6 DBADC 8% Xylene 140 6 2260 6826 3.02 7 DBADC 12%  Xylene 140 6 2049 5805 2.83 8 DBADC 16%  Xylene 140 6 2082 5309 2.55 9 DBADC 20%  Xylene 140 6 1772 4619 2.61 10 DBADC 30%  Xylene 140 6 1761 3664 2.08 11 AIBN 2% Xylene  70 24 3404 7193 2.11 12 AIBN 2% Xylene  70 24 3109 6141 1.98 13 AIBN 2% Xylene  70 24 3500 7295 2.08 14 AIBN 2% Xylene  70 24 3689 6165 1.67

Inventive Example 5 Preparation of Composition comprising Polyacenaphthylene Homopolymer, Thermosetting Component, and Polycarbosilane and Inventive Example 6 Preparation of Composition comprising Polyacenaphthylene Homopolymer and Thermosetting Component

For Inventive Example 5, commercially available polyacenaphthylene homopolymer (25 grams) as porogen, polycarbosilane (CH₂SiH₂)_(q) where q is 20–30 (1.57 grams) (supplied by Starfire Systems, Inc.) as adhesion promoter, and xylene (334 grams) were weighed into a plastic bottle. A stir bar was added to the bottle. The bottle was closed tightly and stirring was activated. The solution was stirred for 24 hours at room temperature. The solution was poured into a pre-weighed 2-neck flask with a stir bar containing thermosetting component (22.43 grams) similar to Preparation 1 or 2 above. The bottle was washed with xylene (approximately 111 grams) and the resulting xylene solution was added to the 2-neck flask until the overall weight of the reaction mixture reached 500 grams. The flask was clamped to a water condenser and the water turned on.

The system was flashed with N₂ (strong stream) from the top of the condenser (inlet) to the side neck (outlet) for 30 minutes. The N₂ inlet on the top of the condenser was replaced to the inlet-outlet and the side neck was closed by a stopper. The weak N₂ stream was continued. The flask was lowered into an oil bath (pre-heated to 145° C. and under constant stirring) to cover the reaction flask. The stir bar was stirring in the reaction flask and the reaction mixture was boiling and left to reflux for 15.5 hours. The heating and stirring were then stopped. The flask was taken out of the oil bath and the flask allowed to cool to room temperature. The stir bar was removed using a magnetic rod and solvent exchange with cyclohexanone started.

Most xylene was removed by rotary evaporator until a viscous liquid was obtained. The remaining reaction mixture weighed about 60 to 90 grams. 500 grams of cyclohexanone was then added to the flask. Again most xylene was then removed by rotary evaporator until a viscous liquid was obtained. The remaining reaction mixture weighed about 60 to 90 grams. This process was repeated two more times to ensure that all xylene was exchanged to cyclohexanone. The solution was then diluted with cyclohexanone to make a 20% solid concentration solution. The solution was filtered slowly at less than 20 pounds per square inch through a 0.1 μm teflon filter. The preceding step was repeated. The final composition was 20% solids with 6.7% weight percent polycarbosilane, 50% weight percent polyacenaphthylene homopolymer, and the remainder was thermosetting component.

For Inventive Example 6, Inventive Example 5 was repeated except that no adhesion promoter was added so that the composition was 50% weight percent polyacenaphthylene homopolymer and the remainder thermosetting component.

Inventive Examples 7–10 Preparation of Composition Comprising Polyacenaphthylene Homopolymer, Thermosetting Component, and Polycarbosilane

For Inventive Example 7, Inventive Example 5 was repeated except that the amount of polycarbosilane (CH₂SiH₂)_(q) where q is 20–30 (supplied by Starfire Systems, Inc.) used was 2.68 grams. The final composition was 20% solids with 12 weight percent polycarbosilane, 50 weight percent polyacenaphthylene homopolymer, and the remainder was thermosetting component. For Inventive Examples 8–10, Inventive Example 7 was repeated except that the weight percent polyacenaphthylene homopolymer was varied as set forth in the following Table 6.

TABLE 6 Polyacenaphthylene Homopolymer Inventive Example Weight Percent 8 35 9 20 10  10

Inventive Examples 11–17 Preparation of Composition Comprising Polyacenaphthylene Homopolymer, Thermosetting Compound, and Polycarbosilane

Inventive Example 5 was repeated except that the amount of polycarbosilane (CH₂SiH₂)_(q) where q is 20–30 (supplied by Starfire Systems, Inc.) used was 1.92 grams. The amount of polyacenaphthylene homopolymer was varied as set forth in the following Table 7.

TABLE 7 Polyacenaphthylene Homopolymer Inventive Example Weight Percent 11 28 12 26.8 13 27.2 14 26.5 15 25.4 16 38.3 17 30.1

Inventive Examples 18–21 Preparation of Composition Comprising Polyacenaphthylene, Homopolymer, Thermosetting Component, and Polycarbosilane

Inventive Example 7 was repeated except that the amount of polyacenaphthylene homopolymer used was 25 weight percent and the polyacenaphthylene homopolymer type used was as set forth in the following Table 8.

TABLE 8 Inventive Example Polyacenaphthylene Homopolymer 18 Table 4 Homopolymer 1 19 Table 4 Homopolymer 2 20 Table 4 Homopolymer 3 21 Table 5 Homopolymer 4

Inventive Examples 22–23 Preparation of Composition Comprising Blend of Polyacenaphthylene Homopolymer, Thermosetting Component, and Ortho-Cresol Novolak

For Inventive Example 22, to 65-mL plastic bottle equipped with a ere added thermosetting component (4.17 grams) similar to Preparation 1 or 2 above, ortho-cresol novolak (0.125 gram) as adhesion promoter, polyacenaphthylene (1.074 grams) as porogen, and cyclohexanone (24.46 grams). The mixture was stirred at room temperature for 2 hours and the homogeneous solution that formed was filtered through 0.1 μm teflon filter. For Inventive Example 23, Inventive Example 22 was repeated except that six weight percent ortho-cresol novolak was used.

Inventive Examples 24–30 Preparation of Composition Comprising Polyacenaphthylene Copolymer, Thermosetting Compound, and Polycarbosilane

For Inventive Example 24, polyacenaphthylene copolymer (4.48 grams; Table 2's Copolymer 13) as porogen, polycarbosilane (CH₂SiH₂)_(q) where q is 20–30 (0.48 gram) as adhesion promoter, and xylenes (59.4 grams) were added to a plastic bottle equipped with a magnetic stirring bar. The solution was stirred at room temperature for 24 hours. The solution was then transferred to a 100 milliliters three neck flask. Thermosetting component (4.00 grams) similar to Preparation 1 or 2 above and an additional 19.8 grams of xylene were added. The solution was flushed with nitrogen for 5 minutes and heated at 145° C. for 15.5 hours. Most xylene was then removed by rotary evaporator until a viscous liquid was obtained. The remaining reaction mixture weighed about 10 to 12 grams. 100 grams of cyclohexanone was then added to the flask. Most solvent was then removed by rotary evaporator until a viscous liquid was obtained. The remaining reaction mixture weighed about 10 to 12 grams. This process was repeated two more times to ensure that all xylene was exchanged to cyclohexanone. The solution was then diluted with cyclohexanone to make a 18% solid concentration solution. The solution was filtered slowly at less than 20 pounds per square inch through a 0.1 μm teflon filter. The preceding step was repeated. The final composition was 18% solids with 12% weight percent polycarbosilane, 50% weight percent polyacenaphthylene copolymer, and the remainder was thermosetting component.

For Inventive Examples 25 through 30, Inventive Example 24 was repeated except that the porogen used is in Table 9 below.

TABLE 9 Inventive Example Table 2 Copolymer 24 7 25 11  26 9 27 6 28 4 29 3 30 1

Inventive Examples 31–32 Preparation of Composition Comprising Polycaprolactone, Thermosetting Compound, and Polycarbosilane

For Inventive Example 31, the solvent used was xylene. Polycaprolactone (4.48 grams) as porogen, polycarbosilane (CH₂SiH₂)_(q) where q is 20–30 (0.48 gram) as adhesion promoter, and xylenes (59.4 grams) were added to a plastic bottle equipped with a magnetic stirring bar. The solution was stirred at room temperature for 24 hours. The solution was then transferred to a 250 milliliter three neck flask. Thermosetting component (4.00 grams) similar to Preparation 1 or 2 above and additional 19.8 grams of xylene were added. The solution was flushed with nitrogen for 5 minutes and heated at 145° C. for 15.5 hours. The solution was filtered slowly at less than 20 pounds per square inch through a 0.1 μm teflon filter. The preceding step was repeated. The final composition was 10% solids with 12% weight percent polycarbosilane, 50% weight percent polycaprolactone, and the remainder was thermosetting component.

For Inventive Example 32, the solvent used was cyclohexanone. Polycaprolactone (4.48 grams) as porogen, polycarbosilane (CH₂SiH₂)_(q) where q is 20–30 (0.48 gram), and xylenes (59.4 grams) were added to a plastic bottle equipped with a magnetic stirring bar. The solution was stirred at room temperature for 24 hours. The solution was then transferred to a 250 milliliters three neck flask. Thermosetting component (4.00 grams) similar to Preparation 1 or 2 above and additional 19.8 grams of xylene were added. The solution was flushed with nitrogen for 5 minutes and heated at 145° C. for 15.5 hours. Most xylene was then removed by rotary evaporator until a viscous liquid was 10 obtained. The remaining reaction mixture weighed about 10 to 12 grams. 100 grams of cyclohexanone was then added to the flask. Again most of the solvent was then removed by rotary evaporator until a viscous liquid was obtained. The remaining reaction mixture weighed about 10 to 12 grams. This process was repeated two more times to ensure that all the xylenes was exchanged to cyclohexanone. The solution was then diluted with cyclohexanone to make a 18% solid concentration solution. The solution was filtered slowly at less than 20 pounds per square inch through a 0.1 μm teflon filter. The preceding step was repeated. The final composition was 18% solids with 12% weight percent polycarbosilane, 50% weight percent polycaprolactone, and the remainder was thermosetting component.

Inventive Examples 33–35 Preparation of Composition Comprising Blend of Polycaprolactone, Thermosetting Compound, and Ortho-Cresol Novolak

Thermosetting component (4.00 grams) similar to Preparation 1 or 2 above, ortho-cresol novolak (0.12 gram; molecular weight of 1760; supplied by Schenectady International Inc.) as adhesion promoter, polycaprolactone (2.53 grams) as porogen, and 37.66 grams of cyclohexanone were added to a plastic bottle equipped with a magnetic stirring bar. The solution was stirred at room temperature for 2 hours. The solution was filtered slowly at less than 20 pounds per square inch through a 0.1 μm teflon filter. The preceding step was repeated. The final composition was 15% solids with 3 weight percent ortho-cresol novolak with respect to the thermosetting component, 35 weight percent polycaprolactone with respect to the total solids, and the remainder being thermosetting component.

This was repeated as follows in Table 10.

TABLE 10 Inventive Example Weight Percent Ortho-Cresol Novolak 33 3.4 34 6.9 35 12.2

Inventive Examples 36–37 Preparation of Composition Comprising Blend of Polyacenaphthylene Homopolymer and Polycaprolactone, Thermosetting Compound, and Polycarbosilane

For Inventive Example 36, the solvent used was xylene. Polycaprolactone (4.48 grams) and commercially available polyacenaphthylene homopolymer (0.7906 gram) as a porogen blend, polycarbosilane (CH₂SiH₂)_(q) where q is 20–30 (0.48 gram) (supplied by Starfire Systems, Inc.) as adhesion promoter, and xylenes (64.74 grams) were added to a plastic bottle equipped with a magnetic stirring bar. The solution was stirred at room temperature for 24 hours. The solution was then transferred to a 250 milliliters three neck flask. Thermosetting component (4.00 grams) similar to Preparation 1 or 2 above and additional xylene (21.58 grams) were added. The solution was flushed with nitrogen for 5 minutes and heated at 145° C. for 15.5 hours. The solution was filtered slowly at less than 20 pounds per square inch through a 0.1 μm teflon filter. The preceding step was repeated. The final composition was 16.5% solids with 12 weight percent polycarbosilane with respect to the thermosetting component, 15 weight percent polyacenaphthylene with respect to the weight of the thermosetting component, and the remainder being thermosetting component.

For Inventive Example 37, the solvent used was cyclohexanone. Polycaprolactone (4.48 grams) and commercially available polyacenaphthylene homopolymer (0.7906 gram) as a porogen blend, polycarbosilane (CH₂SiH₂)_(q) where q is 20–30 (0.48 gram) (supplied by Starfire Systems, Inc.) as adhesion promoter, and xylenes (64.74 grams) were added to a plastic bottle equipped with a magnetic stirring bar. The solution was stirred at room temperature for 24 hours. The solution was then transferred to a 250 milliliters three neck flask. Thermosetting component (4.00 grams) similar to Preparation 1 or 2 above and additional 21.58 grams of xylene were added. The solution was flushed with nitrogen for 5 minutes and heated at 145° C. for 15.5 hours. Most xylene was then removed by rotary evaporator until a viscous liquid was obtained. The remaining reaction mixture weighed about 10 to 12 grams. 100 grams of cyclohexanone was then added to the flask. Again most solvent was then removed by rotary evaporator until a viscous liquid was obtained. The remaining reaction mixture weighed about 10 to 12 grams. This process was repeated two more times to ensure that all the xylenes was exchanged to cyclohexanone. The solution was then diluted with cyclohexanone to make a 18% solid concentration solution. The solution was filtered slowly at less than 20 pounds per square inch through a 0.1 μm teflon filter. The preceding step was repeated.

Inventive Examples 38–41 Preparation of Composition Comprising Blend of Polyacenaphthylene Homopolymer and Polycaprolactone, Thermosetting Compound, and Polycarbosilane

For Inventive Examples 38 and 40, Inventive Example 37 was repeated except that the amount of polycarbosilane was varied as set forth in Table 11. For Inventive Examples 39 and 41, Inventive Example 36 was repeated except the amount of polycarbosilane was varied as set forth in Table 11. In Table 11, PAN stands for polyacenaphthylene homopolymer, PCL stands for polycaprolactone, and PCS stands for polycarbosilane.

TABLE 11 % PAN in Inventive porogen % PCL in Example blend porogen blend % PCS Solvent 38 15 50 6.7 Cyclohexanone 39 15 50 6.7 Xylene 40 15 50 3 Cyclohexanone 41 15 50 3 Xylene

Inventive Example 42 Film Preparation of Inventive Example 5

The composition of Inventive Example 5 was applied to a substrate using typical coating conditions known to those skilled in the art. The resulting spun-on composition was baked for one minute under N₂ (<50 ppm O₂) at each of the following temperatures: 125° C., 250° C., and 300° C. The furnace cure condition was 400° C. for 60 minutes in N₂ (26 liters/minute) with ramping up from 250° C. at 5° K per minute. The cure temperature range was from 350° C. to 450° C. In the composition, the porogen decomposed and the decomposed porogen volatilized whereby pores formed in the composition. The resulting layers were analyzed according to the analytical test methods set forth above and the analyzed resulting layer properties are reported in Table 12 below.

TABLE 12 Parameter Inventive Example 42 Cure Recipe 400° C./2 hours Film Thickness 0.3–1.2 μm Refractive Index n (post bake) 1.6600 Refractive Index n (post cure) 1.3600 Thickness (post bake, nm) 2885.00 Thickness (post cure, nm) 2874.00 Shrinkage % (bake to cure) −0.30 Dielectric Constant (ambient) 1.93 Dielectric Constant (degas) 1.901 Modulus (Gpa) 2.26 ± 0.59 (1.2 μm) Hardness (Gpa) 0.16 ± 0.05 (1.2 μm) Glass Transition Temperature (° C.) >410 (first cycle) Average Peak Pore Diameter  20 nm Average Pore Size Diameter 4.1 nm Pore Volume (cm³/g) 0.557 Film Quality Good Tape Test Passed Stability at 425° C. 4.5%

Inventive Example 43 Film Preparation of Inventive Example 6

The composition of Inventive Example 6 was applied to a substrate using typical coating conditions known to those skilled in the art and using the baking and curing conditions of Inventive Example 42. In the composition, the porogen decomposed and the decomposed porogen volatilized whereby pores formed in the composition. The resulting layer was analyzed according to the analytical test methods set forth above and the analyzed resulting properties are reported in Table 13 below.

TABLE 13 Parameter Inventive Example 43 Refractive Index n (post bake) 1.6600 Refractive Index n (post cure) 1.4150 N² 2.00 Thickness (post bake, nm) 2740.74 Thickness (post cure, nm) 2450.00 Shrinkage % (bake to cure) −10.61 Film Quality Hazy (indicative of phase separation) The Inventive Example 43 results show the benefit of the adhesion promoter presence in Inventive Example 42.

Inventive Examples 44–47 Film Preparation of Inventive Examples 7–10

Each composition of Inventive Examples 7–10 was applied to a substrate using typical coating conditions known to those skilled in the art and using the baking and curing conditions of Inventive Example 42. In each composition, the porogen decomposed and the decomposed porogen volatilized whereby pores formed in the composition. The resulting layers were analyzed according to the analytical test methods set forth above and the analyzed resulting layer properties are reported in Table 14 below.

Scanning Electron Microscope (SEM) results are in FIGS. 4 and 5. FIG. 4 shows the cross section of the film while FIG. 5 shows the surface of the film. As the amount of porogen increased, small pores were observed or visible in the film surface as shown by SEM. Thus, as the amount of porogen decreased, the surface shows less porosity. Also, as the amount of porogen increased, the average pore size diameter increased as shown by the cross section SEM. FIG. 6 has TDMS plots showing that the porogen began to decompose at about 380° C.

TABLE 14 Inventive Inventive Inventive Inventive Parameter Example 44 Example 45 Example 46 Example 47 Porogen 50% 35% 20% 10% Content Adhesion 12% 12% 12% 12% Promoter Cure Recipe 400° C./ 400° C./ 400° C./ 400° C./ 1 hour 1 hour 1 hour 1 hour Film Thickness 0.3–1.2 μm 0.3–1.2 μm 0.3–1.2 μm 0.3–1.2 μm Refractive In- 1.39 1.50 1.56 1.59 dex (RI)n (post cure) (RI)(RI) 1.93 2.25 2.44 2.54 Shrinkage % 11.7 10.5 6.4 4.1 (bake to cure) Dielectric 2.07 2.30 2.54 2.75 Constant (ambient) Dielectric 2.03 2.24 2.46 2.66 Constant (degas) Modulus 2.40 ± 0.121 3.60 ± 0.118 4.80 ± 0.152 5.13 ± 0.192 (Gpa) (1.2 μm) (1.2 μm) (1.2 μm) (1.2 μm) Hardness 0.12 ± 0.018 0.24 ± 0.043 0.33 ± 0.025 0.32 ± 0.037 (Gpa) (1.2 μm) (1.2 μm) (1.2 μm) (1.2 μm) Average Peak 12.0 nm 9.0 nm 5.0 nm 3.0 nm Pore Diameter Average Pore  5.1 nm 4.0 nm 2.8 nm 2.7 nm Size Diameter Pore Volume 0.669 0.511 0.315 0.233 (cm³/g) Porosity Larger pores Macroporous Mostly Microporous microporous Estimated 41 34 24 19 Porosity (%) Surface Area 521 511 450 341 (m²/g) Tape Test Passed Dry/ Passed Dry/ Passed Dry/ Passed Dry/ Wet Wet Wet Wet Stability at 5.45% 5.07% 4.30% 4.07% 425° C.

The results show that the dielectric constant decreased as the amount of porogen added increased.

Inventive Examples 48–54 Film Preparation of Inventive Examples 11–17 and Comparative C

Each composition of Inventive Examples 11–17 was applied to a substrate using typical coating conditions known to those skilled in the art and using the baking and curing conditions of Inventive Example 42. Comparative C was made in a manner similar to the Inventive Examples in our pending U.S. Ser. 60/350,187 filed Jan. 15, 2002 and thus, did not contain porogen. In each composition, the porogen decomposed and the decomposed porogen volatilized whereby pores formed in the composition. The resulting layers were analyzed according to the analytical test methods set forth above and the analyzed resulting layer properties are reported in Table 15.

TABLE 15 Refractive Refractive Shrinkage Dielectric Dielectric Inventive Index Index Thickness Thickness % Constant Constant Example or (post (post (Angstroms) (Angstroms) (after bake k k Comparative baked) cured) (post baked) (post cured) and cure) (ambient) (degas) Δk % 48 1.661 1.529 8518.23 8067.62 −5.29 2.48 2.18 −12.10  49 1.657 1.532 8057.8  7541.79 −6.40 2.51 2.42 −3.59 50 1.661 1.499 7225.37 7093.32 −1.83 2.54 2.44 −3.94 51 1.658 1.521 8659.18 8510.56 −1.72 2.51 2.43 −3.19 52 1.657 1.510 8025.79 7952.16 −0.92 2.53 2.43 −3.95 53 1.659 1.500 8633.55 7815.56 −9.47 2.42 2.33 −3.72 54 1.661 1.504 8899.51 8605.25 −3.31 2.42 2.35 −2.89 C 1.677 1.617 3152.00 3252.00  3.17 2.69 2.62 −2.60 Average Cylindrical Approximate BJH Peak Inventive Surface Area Pore Volume Pore Diameter Pore Diameter Example (m²/g) (cm³/g) (nm) (nm) 48 559.00 0.427 3.10 10.00 49 568.00 0.410 2.90 10.00 50 564.00 0.436 3.10 10.00 51 443.00 0.306 2.80  8.00 52 543.00 0.425 3.10 10.00 53 612.00 0.491 3.20  8.00 54 574.00 0.461 3.20  8.00

Inventive Examples 55–58 Film Preparation of Inventive Examples 18–21 and Comparative D

Each composition of Inventive Examples 18–21 was applied to a substrate using typical coating conditions known to those skilled in the art and using the baking and curing conditions of Inventive Example 42. Comparative D was made in a manner similar to the Inventive Examples in our pending U.S. Ser. 60/350,187 filed Jan. 15, 2002 and thus, did not contain any porogen. In each composition, the porogen decomposed and the decomposed porogen volatilized whereby pores formed in the composition. The resulting layers were analyzed according to the analytical test methods set forth above and the analyzed resulting layer properties are reported in Table 16 below where RI stands for refractive index.

TABLE 16 Inventive Refractive Refractive Thickness Thickness Shrinkage % Example or Index (post Index (post (Angstroms) (Angstroms) (after bake and Comparative baked) cured) (RI)(RI) (post baked) (post cured) cure) 55 1.655 1.548 2.395 6800.55 6916.90 1.71 56 1.657 1.543 2.381 6814.10 6885.99 1.06 57 1.657 1.549 2.400 6792.82 6871.42 1.16 58 1.655 1.567 2.456 7520.50 7394.75 −1.67  D 1.677 1.617 2.615 3152.00 3252.00 3.17 Average Cylindrical Approximate Inventive Surface Area Pore Volume Pore BJH Peak Pore Diameter Example (m²/g) (cm³/g) Diameter (nm) (nm) 57 476 0.31  2.60 16.00 56 464 0.307 2.60 14.00 57 468 0.297 2.50 20.00 58 429 0.275 2.60 20.00

Inventive Examples 59–66 Film Preparation of Inventive Examples 24–30

Each composition of Inventive Examples 24–30 was applied to a substrate using typical coating conditions known to those skilled in the art and using the baking and curing conditions of Inventive Example 42. In each composition, the porogen decomposed and the decomposed porogen volatilized whereby pores formed in the composition. The resulting layers were analyzed according to the analytical test methods set forth above and the analyzed resulting layer properties are reported in Table 17 below.

The results show that the composition comprising porogen of copolymer of acenaphthylene and vinyl pivalate has a lower dielectric constant than a composition comprising porogen of copolymer of acenaphthylene and tert-butyl acrylate.

TABLE 17 Average Starting Shrinkage Cylindrical Approximate Composition: Refractive % Dielectric Dielectric Surface Pore Pore BJH Peak Inventive Inventive Index (post (after bake Refractive Constant k Constant k Area Volume Diameter Pore Diameter Example Example cure) and cure) Index² (ambient) (degas) Δk % (m²/g) (cm³/g) (nm) (nm) 59 26 1.45 16.36 2.10 2.13 2.09 1.88 594 0.651 4.4 11.0 60 27 1.41 11.26 1.99 2.1 2.06 1.90 622 0.698 4.5 14.0 61 28 1.41 8.28 1.99 2.11 2.07 1.90 600 0.697 4.6 12.0 62 29 1.41 9.15 2.00 2.09 2.05 1.91 614 0.696 4.5 11.0 63 30 1.40 5.7 1.95 2.06 2.02 1.94 577 0.738 5.1 16.0 64 31 1.54 25.16 2.36 2.48 2.42 2.42 581 0.389 2.7 No peak 65 32 1.48 17.11 2.18 2.33 2.28 2.15 612 0.504 3.3  7.0 66 33 1.44 12.96 2.07 2.19 2.14 2.28 649 0.631 3.9  9.0

Inventive Examples 67–68 Film Preparation of Inventive Examples 31–32

Each composition of Inventive Examples 31–32 was applied to a substrate using typical coating conditions known to those skilled in the art and using the baking and curing conditions of Inventive Example 42. In each composition, the porogen decomposed and the decomposed porogen volatilized whereby pores formed in the composition. The resulting layers were analyzed according to the analytical test methods set forth above and the analyzed resulting layer properties are reported in Table 18 below where NM means not measured and RI stands for refractive index.

The above was repeated except that the amount of porogen was varied. In Table 19, the results show that a porogen having certain thermal stability properties may be selected to provide a certain desired dielectric constant. In Table 19, RI stands for refractive index.

TABLE 18 Refractive Index Refractive Thickness Thickness Shrinkage % Inventive (post Index (post (Angstroms) (Angstroms) (after bake Example baked) cured) (RI)(RI) (post baked) (post cured) and cure) 67 1.581 1.570 2.466 10819 6275.94 −41.99 68 NM 1.571 2.468 NM NM NM Average Approximate Inventive Surface Area Pore Volume Cylindrical Pore BJH Peak Pore Example (m²/g) (cm³/g) Diameter (nm) Diameter (nm) 67 462 0.25  2.2 Very small 4 nm peak 68  99 0.089 3.6 NM

TABLE 19 Refractive Dielectric Index (post % Thickness Constant k % Porogen Mw cured) (RI)(RI) Change (degas)  0 — 1.613 2.60  4 2.65 27 3000 1.543 2.41 −12 2.49 27 1250 1.568 2.46 −16 — 27  530 1.594 2.54 −19 2.58 35 3000 1.495 2.28 −17 2.44 35 1250 1.556 2.42 −22 2.40 50 3000 1.465 2.15 −31 2.27 50 1250 1.497 2.24 −33 2.24

Inventive Examples 69–71 Film Preparation of Inventive Examples 33–35 and Comparative E

Each composition of Inventive Examples 33–35 was applied to a substrate using typical coating conditions known to those skilled in the art and using the baking and curing conditions of Inventive Example 42. Comparative E was made according to Inventive Examples 4–7 in our pending U.S. Ser. 60/350,187 filed Jan. 15, 2002 and thus, did not contain the present porogen. In each composition, the porogen decomposed and the decomposed porogen volatilized whereby pores formed in the composition. The resulting layers were analyzed according to the analytical test methods set forth above. The layer properties are reported in Table 20 below.

TABLE 20 INVENTIVE INVENTIVE INVENTIVE EXAMPLE EXAMPLE EXAMPLE Compara- PROPERTY 69 70 71 tive E Refractive index 1.542 1.540 1.528 1.623 (post cured) Shrinkage % 16.5 20.4 12.3 5.6 (before curing) K (ambient) 2.58 2.58 2.48 2.73 K (degas) 2.54 2.54 2.43 2.70 Δk % 1.42 1.51 2.09 1.17 Average pore 15 15 33 15 diameter (nm) Pore volume .323 .364 .392 .257 (cm³/g)

Inventive Examples 72–77 Film Preparation of Inventive Examples 38–41 and Comparative F

Each composition of Inventive Examples 38–41 was applied to a substrate using typical coating conditions known to those skilled in the art and using the baking and curing conditions of Inventive Example 42. Comparative F was made in a manner similar to the Inventive Examples in our pending U.S. Ser. 60/350,187 filed Jan. 15, 2002 and thus, did not contain the present porogen. In each composition, the porogen decomposed and the decomposed porogen volatilized whereby pores formed in the composition. The resulting layers were analyzed according to the analytical test methods set forth above and the analyzed resulting layer properties are reported in Table 21 below where NM means not measured and RI stands for refractive index.

TABLE 21 Inventive Refractive Refractive Thickness Thickness Shrinkage % Dielectric Dielectric Example or Index (post Index (post (Angstroms) (Angstroms) (after bake Constant k Constant k Comparative baked) cured) (RI)(RI) (post baked) (post cured) and cure) (ambient) (degas) Δk % 72 1.592 1.549 2.400 10000.36  5980.85 −40.19 2.75 2.61 −5.09 73 NM 1.545 2.387 NM NM NM NM 2.62 −3.16 74 1.595 1.565 2.450 7815.35 4632.49 −40.73 2.78 2.66 −4.32 75 1.601 1.561 2.435 2927.49 1757.16 −39.98 2.76 2.65 −3.99 76 1.603 1.524 2.322 2781.52 1798.23 −35.35 2.53 2.45 −3.16 77 1.603 1.523 2.320 2752.07 1787.38 −35.05 2.60 2.51 −3.46 F 1.677 1.617 — 3152.00 3252.00  3.17 2.69 2.62 −2.60 Inventive Surface Area Pore Volume Average Cylindrical Pore Approximate Example (m²/g) (cm³/g) Diameter (nm) BJH Peak Pore Diameter (nm) 72 507  0.2683 2.1 Small 5 nm peak 73 483 0.23  1.9 Broad 20 nm peak 74 486 0.238 2.0 Very small 17 nm peak 75 482 0.251 2.1 Very small 18 nm peak 76 570 0.394 2.8 Small 8 nm peak 77 550 0.371 2.7 Small 7 nm peak

Inventive Example 78

The separated 1,3/4-bis{1′,3′,5′-tris[3″/4″-(phenylethynyl)phenyl]adamant-7′yl} benzene (shown in FIG. 1F) from Preparation 4 is combined with adhesion promoter and porogen, then dissolved in solvent, spun unto silicon wafers, then baked and cured into a film, and used in a microchip or in a multichip module.

Inventive Example 79

The separated 1,3-bis{3′/4′-[1″,3″,5″-tris[3′″/4′″-(phenylethynyl)phenyl]adamant-7″-yl]phenyl}-5,7-bis[3″″/4″″-(phenylethynyl)phenyl]adamantane (shown in FIG. 1F) from Preparation 5 is combined with adhesion promoter and porogen, then dissolved in solvent, spun unto silicon wafers, then baked and cured into a film, and used in a microchip or in a multichip module. 

1. A composition comprising: (a) a dielectric material; and (b) a porogen comprising at least two fused aromatic rings wherein each of said fused aromatic rings has at least one alkyl substituent thereon and a bond exists between at least two of said alkyl substituents on adjacent aromatic rings, wherein said porogen is a polyacenaphthylene copolymer made from acenaphthylene and a monomer selected from the group consisting of vinyl pivalate; tert-butyl acrylate, 2-vinylnaphthalene; 5-vinyl-2-norbornene; vinyl cyclohexanone; vinyl cyclopentane; 9-vinylanthracene; 4-vinylbiphenyl; tetraphenylbutadiene; stilbene; tert-butylstilbene; indene; allyl-substituted hydridopolycarbosilane; vinyl acetate; methyl acrylate; methyl methacrylate; and vinyl ether, which porogen is present in an amount sufficient to produce uniformly or randomly dispersed pores through the dielectric material when the porogen is degraded.
 2. The composition of claim 1 wherein said dielectric material is organic.
 3. The composition of claim 2 wherein said dielectric material is phenylethynylated-aromatic monomer or oligomer.
 4. The composition of claim 2 wherein said organic dielectric material is a cage compound.
 5. A spin-on precursor comprising said composition of claim
 2. 6. A thermosetting matrix made from said spin-on precursor of claim
 5. 7. A layer comprising said thermosetting matrix of claim
 6. 8. The layer of claim 7 wherein said thermosetting matrix is cured.
 9. A method of using said composition of claim 2 comprising decomposing said porogen.
 10. The method of claim 9 comprising the steps of: decomposing said porogen; and volatilizing said decomposed porogen whereby the dielectric constant of said dielectric material is lowered.
 11. The method of claim 9 comprising the steps of: decomposing said porogen; and volatilizing said decomposed porogen whereby pores form in said dielectric material.
 12. The method of claim 10 wherein said decomposing said porogen step comprises curing by furnace, hot plate, electron beam, microwave, or ultraviolet radiation.
 13. The method of claim 11 wherein said decomposing said porogen step comprises curing by furnace, hot plate, electron beam, microwave, or ultraviolet radiation.
 14. A composition comprising: (a) a dielectric material wherein the dielectric material comprises a cage structure and the dielectric material has a dielectric constant of less than 2.7; and (b) a porogen comprising at least two fused aromatic rings wherein each of said fused aromatic rings has at least one alkyl substituent thereon and a bond exists between at least two of said alkyl substituents on adjacent aromatic rings, which porogen is present in an amount sufficient to produce uniformly or randomly dispersed pores through the dielectric material when the porogen is degraded.
 15. The composition of claim 14 wherein said cage structure is adamantane.
 16. A spin-on precursor comprising said composition of claim
 15. 17. A thermosetting matrix made from said spin-on precursor of claim
 16. 18. A layer comprising said thermosetting matrix of claim
 17. 19. The layer of claim 18 wherein said thermosetting matrix is cured.
 20. A composition comprising: (a) thermosetting component comprising: (1) optionally monomer of Formula

and (2) at least one oligomer or polymer of Formula II

where said E is a cage compound; each of said Q is the same or different and selected from aryl, branched aryl, and substituted aryl wherein said substituents include hydrogen, halogen, alkyl, aryl, substituted aryl, heteroaryl, aryl ether, alkenyl, alkynyl, alkoxyl, hydroxyalkyl, hydroxyaryl, hydroxyalkenyl, hydroxyalkynyl, hydroxyl, or carboxyl; said G is aryl or substituted aryl where substituents include halogen and alkyl; said h is from 0 to 10; said i is from 0 to 10; said j is from 0 to 10; and said w is 0 or 1; (b) a porogen, wherein said porogen comprises a material having a decomposition temperature less than the glass transition temperature of said thermosetting component (a) and greater than the curing temperature of said thermosetting component (a).
 21. The composition of claim 20 wherein said porogen comprises at least two fused aromatic rings wherein each of said fused aromatic rings has at least one alkyl substituent thereon and a bond exists between at least two of said alkyl substituents on adjacent aromatic rings.
 22. The composition of claim 20 wherein said porogen is selected from the group consisting of unfunctionalized polyacenaphthylene homopolymer, functionalized polyacenaphthylene homopolymer, polyacenaphthylene copolymer, polynorbornene, polycaprolactone, poly(2-vinylnaphthalene), vinyl anthracene, polystyrene, polystyrene derivatives, polysiloxane, polyester, polyether, polyacrylate, aliphatic polycarbonate, polysulfone, polylactide, and blends thereof.
 23. The composition of claim 22 wherein said porogen is acenaphthylene copolymer made from acenaphthylene and monomer selected from the group consisting of vinyl pivalate; tert-butyl acrylate; styrene; α-methylstyrene; tert-butylstyrene; 2-vinylnaphthalene; 5-vinyl-2-norbornene; vinyl cyclohexanone; vinyl cyclopentane; 9-vinylanthracene; 4-vinylbiphenyl; tetraphenylbutadiene; stilbene; tert-butylstilbene; indene; allyl-substituted hydridopolycarbosilane; vinyl acetate; methyl acrylate; methyl methacrylate; and vinyl ether.
 24. The composition of claim 20 wherein said porogen is selected from the group consisting of unfunctionalized polyacenaphthylene homopolymer, functionalized polyacenaphthylene homopolymer, polyacenaphthylene copolymer, polynorbornene, and polycaprolactone.
 25. The composition of claim 22 wherein said thermosetting component (a) comprises (1) adamantane monomer of Formula III

and (2) adamantane oligomer or polymer of Formula IV

or (1) diamantane monomer of Formula V

and (2) diamantane oligomer or polymer of Formula VI

where said h is from 0 to 10; said i is from 0 to 10; said j is from 0 to 10; each of said R₁ is the same or different and selected from hydrogen, halogen, alkyl, aryl, substituted aryl, heteroaryl, aryl ether, alkenyl, alkynyl, alkoxyl, hydroxyalkyl, hydroxyaryl, hydroxyalkenyl, hydroxyalkynyl, hydroxyl, or carboxyl; and each of said Y is same or different and is selected from hydrogen, alkyl, aryl, substituted aryl, or halogen.
 26. The composition of claim 25 wherein said adamantane monomer of Formula III is present.
 27. The composition of claim 25 or 26 wherein said R₁ is aryl or substituted aryl and said Y is hydrogen, phenyl, or biphenyl.
 28. The composition of claim 27 wherein said (2) adamantane oligomer or polymer is dimer of Formula IX

or said (2) diamantane oligomer or polymer is dimer of Formula X


29. The composition of claim 27 wherein said (2) adamantane oligomer or polymer is trimer of Formula XI

or said (2) diamantane oligomer or polymer is trimer of Formula XII


30. The composition of claim 27 where in said thermosetting component (a), said oligomer or polymer (2) comprises a mixture of adamantane dimer of Formula IX

and adamantane trimer of Formula XI

or diamantane dimer of Formula X

and diamantane trimer of Formula XII


31. The composition of claim 30 where in said thermosetting component (a), said monomer (1) and said oligomer or polymer (2) are adamantane based monomers.
 32. The composition of claim 31 wherein at least two of said R₁C≡C groups on said phenyl groups are two different isomers and at least one of said phenyl groups between two bridgehead carbons of said adamantane monomers exists as two different isomers.
 33. The composition of claim 32 wherein said at least two isomers are meta- and para- isomers.
 34. The composition of claim 27 additionally comprising (c) adhesion promoter comprising compound having at least bifunctionality wherein the bifunctionality may be the same or different and the first functionality is capable of interacting with said thermosetting component (a) and the second functionality is capable of interacting with a substrate when said composition is applied to said substrate.
 35. The composition of claim 34 wherein said adhesion promoter is selected from the group consisting of: silanes of the Formula XXIV: (R₂)_(k)(R₃)_(l)Si(R₄)_(m)(R₅)_(n) wherein R₂, R₃, R₄, and R₅ each independently represents hydrogen, hydroxyl, unsaturated or saturated alkyl, substituted or unsubstituted alkyl where the substituent is amino or epoxy, unsaturated or saturated alkoxyl, unsaturated or saturated carboxylic acid radical, or aryl, at least two of said R₂, R₃, R₄, and R₅ represent hydrogen, hydroxyl, saturated or unsaturated alkoxyl, unsaturated alkyl, or unsaturated carboxylic acid radical, and k+l+m+n≦4; polycarbosilane of the Formula XXV:

in which R₈, R₁₄, and R₁₇ each independently represents substituted or unsubstituted alkylene, cycloalkylene, vinylene, allylene, or arylene; R₉, R₁₀, R₁₁, R₁₀, R₁₅, and R₁₆ each independently represents hydrogen atom or organo group comprising alkyl, alkylene, vinyl, cycloalkyl, allyl, or aryl and may be linear or branched; R₁₃, represents organosilicon, silanyl, siloxyl, or organo group; and p, q, r, and s satisfy the conditions of [4≦p+q+r+s≦100,000], and q and r and s may collectively or independently be zero; glycidyl ethers, or esters of unsaturated carboxylic acids containing at least one carboxylic acid group; vinyl cyclic oligomers or polymers where the cyclic group is vinyl, aromatic, or heteroaromatic; and phenol-formaldehyde resins or oligomers of the Formula XXVI: —[R₁₈C₆H₂(OH)(R₁₉]_(u) where R₁₈ is substituted or unsubstituted alkylene, cycloalkylene, vinyl, allyl, or aryl, R₁₉ is alkyl, alkylene, vinylene, cycloalkylene, allylene, or aryl, and u=3–100.
 36. The composition of claim 35 wherein said adhesion promoter (c) is said phenol-formaldehyde resin or oligomer.
 37. A spin-on precursor comprising said composition of claim 34 and solvent.
 38. A thermosetting matrix made from said spin-on precursor of claim
 37. 39. A layer comprising said thermosetting matrix of claim
 38. 40. The layer of claim 39 wherein said thermosetting matrix is cured.
 41. The layer of claim 39 wherein said layer has a dielectric constant of less than 2.7.
 42. The layer of claim 39 wherein said layer has an average pore size diameter of less than 20 nanometers.
 43. A substrate having thereon at least one of said layer of claim
 39. 44. A microchip comprising said substrate of claim
 43. 45. A composition comprising: (a) a compound having at least bifunctionality wherein the bifunctionality may be the same or different and at least one of a first functionality and a second functionality is selected from the group consisting of Si containing groups; N containing groups; C bonded to O containing groups; hydroxyl groups; and C double bonded to C containing groups; and (b) a porogen comprising at least two fused aromatic rings wherein each of said fused aromatic rings has at least one alkyl substituent thereon and a bond exists between at least two of said alkyl substituents on adjacent aromatic rings, wherein said porogen is polyacenaphthylene copolymer made from acenaphthylene and monomer selected from the group consisting of vinyl pivalate; tert-butyl acrylate; 2-vinylnaphthalene; 5-vinyl-2-norbornene; vinyl cyclohexanone; vinyl cyclopentane; 9-vinylanthracene; 4-vinylbiphenyl; tetraphenylbutadiene; stilbene; tert-butylstilbene; indene; allyl-substituted hydridopolycarbosilane; vinyl acetate; methyl acrylate; methyl methacrylate; and vinyl ether; which porogen is present in an amount sufficient to produce uniformly or randomly dispersed pores through the dielectric material when the porogen is degraded.
 46. The composition of claim 45 further comprising an adhesion promoter selected from the group consisting of: silanes of the Formula XXIV: (R₂)_(k)(R₃)_(l)Si(R₄)_(m)(R₅)_(n) wherein R₂, R₃, R₄, and R₅ each independently represents hydrogen, hydroxyl, unsaturated or saturated alkyl, substituted or unsubstituted alkyl where the substituent is amino or epoxy, unsaturated or saturated alkoxyl, unsaturated or saturated carboxylic acid radical , or aryl, at least two of said R₂, R₃, R₄, and R₅ represent hydrogen, hydroxyl, saturated or unsaturated alkoxyl, unsaturated alkyl, or unsaturated carboxylic acid radical, and k+l+m+n≦4; polycarbosilane of thy Formula XXV:

in which R₈, R₁₄, and R₁₇ each independently represents substituted or unsubstituted alkylene, cycloalkylene, vinylene, allylene, or arylene; R₉, R₁₀, R₁₁, R₁₀, R₁₅, and R₁₆ each independently represents hydrogen atom or organo group comprising alkyl, alkylene, vinyl, cycloalkyl, allyl, or aryl and may be linear or branched; R₁₃ represents organosilicon, silanyl, siloxyl, or organo group; and p, q, r, and s satisfy the conditions of [4≦p+q+r+s≦100,000], and q and r and s may collectively or independently be zero; glycidyl ethers, or esters of unsaturated carboxylic acids containing at least one carboxylic acid group; vinyl cyclic oligomers or polymers where the cyclic group is vinyl, aromatic, or heteroaromatic; and phenol-formaldehyde resins or oligomers of the Formula XXVI: —[R₁₈C₆H₂(OH)(R₁₉]_(u) where R₁₈ is substituted or unsubstituted alkylene, cycloalkylene, vinyl, allyl, or aryl, R₁₉ is alkyl, alkylene, vinylene, cycloalkylene, allylene, or aryl, and u3–100.
 47. The composition of claim 46 wherein said adhesion promoter (c) is said phenol-formaldehyde resin or oligomer.
 48. The composition of claim 46 wherein said compound (a) and said porogen (b) interact.
 49. The composition of claim 46 additionally comprising dielectric material. 